Composition based on halogenated resins
19 claims: 7 independent, 12 dependent
- 1Utwardzalna przez sieciowanie kompozycja chlorowcowanej żywicy polisiloksanowej, znamienna tym, że zawiera co najmniej jeden półprodukt silikonowy;PL 193 083 B1 żywicę wybraną spośród grupy obejmującej żywice z hydroksylowymi i epoksydowymi grupami funkcyjnymi;składnik organiczny zawierający chlorowiec posiadający co najmniej jedną grupę funkcyjną wybraną z grupy obejmującej grupę hydroksylową, aminową i karboksylową;oraz utwardzacz aminowy.
- 2Kompozycja według zastrz. 1, znamienna tym, że zawiera półprodukt silikonowy wybrany spośród grupy obejmującej półprodukty silikonowe z hydroksylowymi i alkoksylowymi grupami funkcyjnymi, o wzorze -Rl2 η w którym każdy R10 i R11 jest niezależnie wybrany z grupy obejmującej grupę hydroksylową, grupy alkilową, arylową i alkoksylową, zawierające do sześciu atomów węgla, każda z grup R9 i R12 jest niezależnie wybrana z grupy obejmującej atom wodoru, grupę alkilową i arylową, zawierające do 12 atomów węgla, zaś n jest dobrane tak, że średnia ważona masa cząsteczkowa półproduktu silikonowego mieści się w zakresie od około 100do 10000.
- 3Kompozycja według zastrz. 1, znamienna tym, że zawiera półprodukt silikonowy o wzorze w którym R13 jest wybrany z grupy obejmującej grupę alkilową, arylową i alkoksylową, w którym R14 i R15 są wybrane z grupy obejmującej grupę alkilową, arylową i alkoksylową, R16 stanowi grupę alkilową, zaś n1 jest tak dobrany, że średnia ważona masa cząsteczkowa żywicy siloksanowej mieści sięw zakresie od około 500 do 5000.
- 4Kompozycja według zastrz. 1, znamienna tym, że zawiera katalizator wybrany z grupy obejmującej związki metaloorganiczne, kwasy, zasady i ich mieszaniny.
- 5Utwardzalna przez sieciowanie kompozycja chlorowcowanej żywicy polisiloksanowej, znamienna tym, że zawiera co najmniej jeden półprodukt silikonowy wybrany spośród grupy obejmującej półprodukty silikonowe z hydroksylowymi i alkoksylowymi grupami funkcyjnymi;żywicę wybraną spośród grupy obejmującej żywice z hydroksylowymi i epoksydowymi grupami funkcyjnymi;składnik organiczny zawierający chlorowiec posiadający co najmniej jedną grupę funkcyjną wybraną z grupy obejmującej grupę hydroksylową, aminową i karboksylową;co najmniej jeden silan wybrany z grupy obejmującej silany aryloalkoksylowe, silany alkiloalkoksylowe, chlorowcowane silany i ich mieszaniny.
- 6Kompozycja według zastrz. 5, znamienna tym, że zawiera półprodukt silikonowy o wzorze -Ri2 η w którym każdy z R10 i R11 jest niezależnie wybrany z grupy obejmującej grupę hydroksylową, grupy alkilową, arylową i alkoksylową, zawierające do sześciu atomów węgla, każdy z R9 i R12 jest niezależnie wybrany z grupy obejmującej atom wodoru, grupę alkilową i arylową, zawierające do PL 193 083 B1 12 atomów węgla, zaś n jest dobrane tak, że średnia masa cząsteczkowa półproduktu silikonowego mieści się w zakresie od około 100 do 10000.
- 7Kompozycja według zastrz. 5, znamienna tym, że zawiera półprodukt silikonowy o wzorze w którym R13 jest wybrany z grupy obejmującej grupę alkilową, arylową i alkoksylową, R14 i R15 są wybrane z grupy obejmującej grupę alkilową, arylową i alkoksylową, R16 stanowi grupę alkilową, zaś n1 jest tak dobrany, że średnia ważona masa cząsteczkowa żywicy siloksanowej mieści się w zakresie od około 500 do 5000.
- 8Kompozycja według zastrz. 5, znamienna tym, że zawiera silan aryloalkoksylowy o wzorze w którym R1 oznacza grupę arylową, zaś każda z grup R2, R3 i R4 oznacza grupę alkoksylową zawierającą mniej niż cztery atomy węgla, o średniej masie cząsteczkowej w zakresie od 150 do 300.
- 9Kompozycja według zastrz. 5, znamienna tym, że zawiera silan alkoksyalkilowy o wzorze w którym R5 oznacza grupę alkilową zawierającą poniżej czterech atomów węgla, zaś każdy z R6, R7 i R8 oznacza grupę alkoksylową zawierającą poniżej czterech atomów węgla, o średniej masie cząsteczkowej mieszczącej się w zakresie od 100 do 300.
- 10Utwardzalna przez sieciowanie kompozycja chlorowcowanej żywicy polisiloksanowej, znamienna tym, że zawiera co najmniej jeden półprodukt silikonowy wybrany spośród grupy obejmującej półprodukty silikonowe z hydroksylowymi i alkoksylowymi grupami funkcyjnymi, o wzorze -Rl2 η w którym każdy z R10 i R11 jest niezależnie wybrany z grupy obejmującej grupę hydroksylową, grupy alkilową, arylową i alkoksylową, zawierające do sześciu atomów węgla, każdy z R9 i R12 jest niezależnie wybrany z grupy obejmującej atom wodoru, grupę alkilową i arylową zawierające do 12 atomów węgla, zaś n jest dobrane tak, że średnia ważona masa cząsteczkowa półproduktu silikonowego wynosi od około 100 do 10000;żywicę wybraną z grupy obejmującej żywice akrylowe, żywice poliestrowe, żywice epoksydowe, żywice fenolowe i żywice fenolowo sianowe;składnik organiczny zawierający chlorowiec posiadający co najmniej jedną grupę funkcyjną wybraną z grupy obejmującej grupę hydroksylową, aminową i karboksylową;PL 193 083 B1 jeden lub więcej utwardzaczy aminowych oraz katalizatorów, przy czym katalizator jest wybrany spośród grupy obejmującej związki metaloorganiczne, kwasy, zasady i ich mieszaniny;co najmniej jeden silan wybrany z grupy obejmującej silany aryloalkoksylowe, silany alkiloalkoksylowe, chlorowcowane silany i ich mieszaniny.
- 11Kompozycja według zastrz. 10, znamienna tym, że zawiera dodatkowy półprodukt silikonowy o wzorze w którym R13 jest wybrany z grupy obejmującej grupę alkilową, arylową, i alkoksylową, R14 i R15 są wybrane z grupy obejmującej grupą alkilową, arylową i alkoksylową, w którym R16 stanowi grupę alkilową, zaś n1 jest tak dobrany, że średnia ważona masa cząsteczkowa żywicy siloksanowej mieści się w zakresie od około 500 do 5000.
- 12Kompozycja według zastrz. 10, znamienna tym, że zawiera aminowy utwardzacz, który jest aminosilanem o wzorze Y-Si-(O-X)3 w którym Y oznacza H(HNR17)a i „a oznacza liczbę całkowitą od dwa do siedem, każdy z R17 oznacza dwufunkcyjny rodnik organiczny niezależnie wybrany z grupy obejmującej rodniki arylowy, alkilowy, dialkiloarylowy, alkoksyalkilowy i cykloalkilowy, R17 może zmieniać się dla każdej cząsteczki Y, zaś każdy X może być taki sam lub różny i wybrany jest z grupy obejmującej grupę alkilową, hydroksyalkilową, alkoksyalkilową i hydroksyalkoksyalkilową, zawierające mniej niż około sześciu atomów węgla.
- 13Kompozycja chlorowcowanej żywicy polisiloksanowej, znamienna tym, że zawiera zasadniczo co najmniej jeden półprodukt silikonowy wybrany spośród grupy obejmującej półprodukty silikonowe z hydroksylowymi i alkoksylowymi grupami funkcyjnymi;żywicę wybraną spośród grupy obejmującej żywice z hydroksylowymi i epoksydowymi grupami funkcyjnymi;składnik organiczny zawierający chlorowiec posiadający co najmniej jedną grupę funkcyjną wybraną z grupy obejmującej grupę hydroksylową, aminową i karboksylową;co najmniej jeden silan wybrany z grupy obejmującej silany aryloalkoksylowe, silany alkiloalkoksylowe, chlorowcowane silany i ich mieszaniny.
- 14Sposób wytwarzania kompozycji chlorowcowanej żywicy polisiloksanowej, znamienny tym, że łączy się co najmniej jeden półprodukt silikonowy;z żywicą wybraną z grupy obejmującej żywice z hydroksylowymi i epoksydowymi grupami funkcyjnymi tworząc mieszaninę;składnikiem organicznym zawierającym chlorowiec i posiadającym grupę funkcyjną wybraną z grupy aminowej, hydroksylowej i karboksylowej ;aminowym utwardzaczem, a następnie przeprowadza się reakcję składników mieszaniny sieciując chlorowcowaną kompozycję żywicy polisiloksanowej.
- 15Sposób według zastrz. 14, znamienny tym, że reakcję przeprowadza się w temperaturze otoczenia w obecności wody.
- 16Sposób wytwarzania kompozycji chlorowcowanej żywicy polisiloksanowej, znamienny tym, że łączy się co najmniej jeden półprodukt silikonowy wybrany spośród grupy obejmującej półprodukty silikonowe z hydroksylowymi i alkoksylowymi grupami funkcyjnymi;z żywicą wybraną z grupy obejmującej żywice z hydroksylowymi i epoksydowymi grupami funkcyjnymi tworząc mieszaninę;PL 193 083 B1 składnikiem organicznym zawierającym chlorowiec i posiadającym grupę funkcyjną wybraną z grupy aminowej, hydroksylowej i karboksylowej;co najmniej jednym silanem wybranym z grupy obejmującej silany aryloalkoksylowe, silany alkiloalkoksylowe i chlorowcowane silany;oraz jednym lub więcej utwardzaczy aminowych oraz katalizatorów, przy czym katalizator jest wybrany spośród grupy obejmującej związki metaloorganiczne, kwasy, zasady i ich mieszaniny;tworząc mieszaninę;a następnie przeprowadza się reakcję składników mieszaniny sieciując chlorowcowaną kompozycję żywicy polisiloksanowej.
- 17Sposób według zastrz. 16, znamienny tym, że reakcję przeprowadza się w temperaturze otoczenia.
- 18Sposób wytwarzania kompozycji chlorowcowanej żywicy polisiloksanowej, znamienny tym, że tworzy się chlorowcowany organooksysilan przeprowadzając reakcję jednego lub większej liczby półproduktów silikonowych wybranych z grupy obejmującej półprodukty silikonowe zawierające hydroksylowe i alkoksylowe grupy funkcyjne, z silanem i składnikiem organicznym zawierającym chlorowiec i hydroksylowe grupy funkcyjne oraz ze składnikiem wybranym z grupy obejmującej trzeciorzędowe aminy, aminosilany, związki metaloorganiczne, kwasy, zasady i ich mieszaniny, po czym przeprowadzając polikondensację połączonych składników z wytworzeniem usieciowanego chlorowcowanego organooksysilanu;następnie przeprowadza się kondensację chlorowcowanego organooksysilanu z żywicą wybraną z grupy obejmującej żywice z hydroksylowymi i epoksydowymi grupami funkcyjnymi z wytworzeniem usieciowanej chlorowcowanej żywicy polisiloksanowej.
- 19Sposób według zastrz. 18, znamienny tym, że kondensację przeprowadza się w temperaturze otoczenia.
Independent claims19
153 paragraphs in 5 sections, as filed
Description of the invention
Scope of the Invention
The present invention relates to halogenated resin compositions and methods of making some of them, more particularly halogenated polysiloxane resin compositions produced without the use of halogen acids having improved properties of resistance to ultraviolet light, weathering, improved chemical, corrosion and abrasion resistance, refractoriness, hydrophobicity and adhesion. to the material (substrate).
The basis of the invention
The halogenated resin compositions are useful in the preparation of a variety of products such as protective coatings, mechanical items, and the like due to their excellent physical properties of resistance to chemicals, corrosion, weathering, and ultraviolet light. Compositions based on halogenated resins obtained from silicon-containing polymers provide the products made therewith with further improved physical properties such as increased flexibility and impact resistance, especially desirable for products subjected to some degree of movement or bending, or subjected to some degree of impact.
Halogenated resin compositions are typically prepared by reacting a specific polymer, such as a silicon-containing polymer, with a halogen acid. Selected halogen acids include, for example, hydrofluoric, hydrochloric or hydrobromic acid, depending on which of the above-mentioned properties are to be improved. The halogen acid reacts with the designated polymer to introduce one or more halogen groups into its molecule, resulting in a halogenated composition with improved or improved properties.
Halogen acids are known to be both corrosive and toxic, and therefore the use of these acids in the preparation of halogenated compositions poses a serious risk to health and the environment if appropriate precautions are not taken. In addition to the possible health and environmental hazards, it is necessary to use an additional step and additional equipment to ensure the safe handling of such chemicals during the production process, which increases the costs of the process and the final product and extends the time of its production.
Conventional halogenated resin compositions are useful, for example, as protective coatings for objects such as metal, glass, and the like as they increase chemical and weather resistance. The materials are coated with such conventional halogenated resin compositions typically by spraying, and initially to facilitate this, the compositions are diluted with an organic solvent. The use of organic solvents to dilute or thin chemical compositions is regulated by state and / or federal regulations due to the presence of volatile organic compounds (VOC) in these solvent-containing compositions and the accompanying release of volatile components into the environment. Accordingly, there is a need for halogenated resin compositions that are manufactured under state and / or federal VOC laws.
Therefore, it is desirable that the halogenated resin compositions be prepared by a process without the need for potentially hazardous halogen acids. It is desirable that the halogenated resin compositions thus obtained exhibit the same or better chemical, corrosion, weather, heat and fire, and ultraviolet light resistance as compared to halogenated resin compositions prepared with halogen acids. It is desirable that such halogenated resin compositions be suitable for use as protective coatings and the like, and meet existing state and federal VOC standards. It is also desirable that such halogenated resin compositions be prepared from commercially available ingredients.
Summary of the invention
The present invention provides halogenated polysiloxane resin compositions, and methods of making some of them without the need for halogen acids, and having excellent properties of impact, bending, chemical, corrosion, weathering, temperature and fire, abrasion, ultraviolet light, and ultraviolet light. hydrophobicity and adhesion to the material.
Halogenated polysiloxane resin compositions are prepared in accordance with the principles of the present invention by combining: at least one silicone intermediate selected from the group consisting of
Silicone resins with hydroxy and alkoxy functions with a silane selected from the group consisting of aralkoxy silanes, alkylalkoxy silanes, halogenated silanes, and mixtures thereof; and a halogen-containing organic component having functional groups selected from hydroxyl, amino and carboxyl groups; and a resin selected from the group of resins with hydroxyl and epoxy functionality. If desired, an amine hardener and / or a catalyst selected from the group consisting of organometallic compounds, acids, bases and mixtures thereof are added to the mixture to facilitate the reaction and harden the resulting composition at ambient temperature. When the component is an acrylic or polyester resin, the silicone intermediate may be an alkylalkoxy siloxane.
Mixed in the right proportions with proper mixing and temperature, the silicone intermediate, the selected silane, and the halogen-containing components undergo hydrolysis and condensation reactions to produce a halogenated organoxysilane which further condenses with itself and with other hydrolyzed compounds to form a cross-linked halogenated organoxysilane composition. The resin component condenses with the condensing halogenated organoxysilane, inserting into the skeleton of the cross-linked halogenated polysiloxane polymer, thereby forming a halogenated polysiloxane resin composition. The composition is prepared without the use of potentially hazardous inorganic halogen acids, and is either fully cured at ambient temperature under the action of atmospheric moisture, or can be cured at elevated temperatures.
Brief description of the drawings
These and other special features and advantages will be appreciated and will be better understood from the description, claims and drawings, of which the attached drawing shows a one-dimensional axonometric view of a filament (filament) of a tube made of turns of filaments connected together by a halogenated resin composition. polysiloxane prepared according to the present invention.
Detailed description
The present invention relates to halogenated polysiloxane resin compositions prepared by combining a halogen-containing compound with at least one silicone intermediate. Halogenated polysiloxane resin compositions are obtained without the use of halogen acids and can be used in the preparation of coatings, adhesives (binders), composites and the like, or can be further combined with organic polymers such as epoxy, acrylic, polyester, phenolic resins and the like. obtaining halogenated polysiloxane resin compositions. The halogenated polysiloxane resin compositions prepared according to the present invention have the same or better chemical, corrosion, weathering, heat and fire, and ultraviolet light resistance compared to halogenated resin compositions made with halogen acids.
Halogenated polysiloxane resin compositions are produced without the use of halogen acids by combining:
(a) one or more selected silanes; with (b) at least one hydroxy or alkoxy functional silicone intermediate; (c) a resin containing a hydroxyl or epoxy function; and (d) a halogen-containing organic component; with the following optional ingredients:
(i) an amine hardener; and (ii) at least one catalyst.
Solvents, conventional fillers and dyes, plasticizers, flow additives, wetting agents, and the like can be added to the composition to achieve beneficial properties for a particular application. Generally speaking, the ingredients combine and undergo hydrolysis and polycondensation reactions to produce a halogenated organoxysilane polymer which reacts with the resin to form halogenated polysiloxane resin compositions.
With respect to the suitable silane component, useful silanes include silanes selected from the group consisting of alkylalkoxy silanes, aralkoxy silanes, halogenated silanes, and mixtures thereof. In an exemplary embodiment, the halogenated acrylic or polyester polysiloxane resin compositions are prepared using an aralkoxy silane. Suitable arylalkoxy silanes include silanes of the general formula
PL 193 083 B1
<img file="PL193083B1_D0001.tif" />
wherein R1 is an aryl group in which R2, R3 and R4 are each alkoxy containing less than four carbon atoms, where each R2,
R3 and R4 may be the same or different, and having an average molecular weight ranging from about 150 to 300. A preferred aralkoxy silane is one in which R2, R3, and R4 are each methoxy to facilitate the hydrolysis and condensation reaction. A particularly preferred aralkoxy silane is phenyltrimethoxy silane available from Dow Corning, of Midland, Michigan under the product name Z-6124; and a mixture of phenyltrimethoxy silane and phenylmethyldimethoxy silane available, e.g. from Wacker Silicones Corporation of Adrian, Michigan under the product name SY-201.
The aralkoxy silane component is used to improve the conformability of the acrylic or polyester resin and other organic chemical components and to improve the thermal resistance of the final composition. A preferred halogenated acrylic or polyester polysiloxane resin composition is prepared using up to about 15 weight percent of an aralkoxy silane based on the total weight of the composition. The use of greater than 15 percent by weight of the arylalkoxy silane may result in the final cured composition being too soft for certain applications such as protective coatings, which would have surface damage and punctures.
While it is understood to use such aralkoxy silanes in the preparation of halogenated acrylic or polyester polysiloxane resin compositions, they may also be used in the preparation of halogenated epoxy or phenolic polysiloxane resin compositions in an amount of up to about eight percent by weight based on the total weight of the composition.
The halogenated polysiloxane resin compositions of the present invention are also prepared from an alkylalkoxy silane. It should be understood that either the alkylalkoxy silane alone or in combination with an aralkoxy silane can be used to prepare the halogenated acrylic or polyester polysiloxane resin compositions. Suitable alkylalkoxy silanes are those which have the general formula
<img file="PL193083B1_D0002.tif" />
wherein R5 is an alkyl group of less than four carbon atoms, wherein R6, R7 and R8 are each alkoxy of less than four carbon atoms, and have an average molecular weight ranging from 100 to 300.
A preferred alkylalkoxy silane is one in which each R6, R7 and R8 is a methoxy group to facilitate the hydrolysis and condensation reaction. A preferred alkylalkoxy silane is methyltrimethoxy silane available, for example, from OSI Specialties of Tarrytown, New York under the name Silquest A-163; from Dow Corning under the product name Z-6070 and from Huls America of Pitscataway, New Jersey under the product name Dynasylan MTMS.
The alkylalkoxy silane is used in the preparation of the halogenated resin composition to increase the chemical resistance and hydrophobicity of the final composition, and to suppress the effect of the arylalkoxy silane also added. A preferred halogenated resin composition is prepared using up to about 15 weight percent of the alkylalkoxy silane based on the total weight of the composition, more preferably up to ten weight percent of the alkylalkoxy silane. The use of greater than 15 weight percent of the alkylalkoxy silane can result in a cured coating that is too brittle for certain applications such as, for example, as a protective coating.
The halogenated polysiloxane resin compositions of the present invention are also prepared using a halogenated silane. It should be understood that the halogenated silane may be used in combination with two or only one alkylalkoxy silane or arylalkoxy silane for the preparation of halogenated polysiloxane resin compositions. Suitable halogenated silanes are fluorinated or chlorinated silanes containing less than about 15 carbon atoms. Such silanes are needed because they increase the abrasion resistance, chemical resistance, hydrophobicity, weather resistance and flame inhibition of the final composition.
A preferred halogenated silane is 1,1,1-trifluoropropyltrimethoxy silane available, for example, from Dow Corning under the product name Q3-9030. The halogenated silane is used to prepare the halogenated resin composition to increase the abrasion and weather resistance of the final composition. Up to 15 weight percent of halogenated silane based on total weight of the composition is used to prepare the halogenated polysiloxane resin compositions of the present invention, and more preferably up to ten weight percent of halogenated silane is used. The use of greater than about 15 weight percent of halogenated silane is undesirable as this may result in an overly brittle final cured composition.
With respect to the silicone intermediate, suitable materials are those selected from the group consisting of hydroxyl and alkoxy functional silicone intermediates. It should be understood that one or more different silicone intermediates may be used to obtain the halogenated polysiloxane resin composition of the present invention, and that the type or types of material used depends on the nature of the hydroxy or epoxy resin. Suitable hydroxy and alkoxy functional silicone intermediates are those having the general formula
<img file="PL193083B1_D0003.tif" />
wherein each of R10 and R11 is independently selected from the group consisting of hydroxy, alkyl, aryl, and alkoxy of up to about six carbon atoms, wherein each of R9 and R12 is independently selected from the group consisting of hydrogen, and alkyl and aryl containing up to about 12 carbon atoms, and where "n" is selected such that the average molecular weight of the silicone intermediate is in the range of about 100 to 10,000.
It is required that at least one of the groups R10 and R11 be alkoxy or hydroxy as this facilitates the hydrolysis and condensation reactions. Where the R10 and R11 groups are alkoxy, it is desirable that each of them contain no more than about six carbon atoms, which facilitates rapid evaporation of the length-analogous alcohol formed during hydrolysis and promotes complete hydrolysis and polycondensation. Certain of the R10 and R11 groups are phenyl when required to achieve heat and high temperature resistance.
Preferred hydroxy- and alkoxy-functional silicone intermediates are those available e.g. from Dow Corning under the names DC-804, DC-840, DC-Z6018, DCI-2530, DC6-2230, DC-3037, DC-3074, QI- 2530 (hydroxyl-functional phenylmethyl silicone intermediate), and QI-2230 (methoxy-functional methyl phenylmethyl silicone intermediate); and from Wacker Silicones products named SY-231 (Phenylmethyl Silicone Intermediate), SY-550 and SY-430.
Hydroxy and alkoxy functional silicone intermediates are used in the preparation of halogenated resin compositions as they impart desirable characteristics to inorganic chemicals such as increased heat resistance, chemical and weather resistance and increased hydrophobicity. A preferred halogenated polysiloxane resin composition is prepared using a hydroxy and alkoxy functional silicone intermediate in an amount ranging from 10 to 70 weight percent based on the total weight of the composition, and more preferably ranging from about 15 to 45 weight percent containing hydroxy and alkoxy functions. silicone semi-finished product.
Use of less than about ten weight percent of the hydroxy- and alkoxy-functional silicone intermediate can result in a halogenated polysiloxane resin composition.
Lacking the required chemical, thermal and weather resistance. The use of greater than about 70 weight percent of the hydroxy-alkoxy functional silicone intermediate may provide the halogenated polysiloxane resin composition too brittle or too hard for practical use as a protective coating.
Where the hydroxylated or epoxidized resin is an acrylic or polyester resin, the desired alkoxy-functional silicone intermediate is a compound of the general formula
<img file="PL193083B1_D0004.tif" />
where R13 is selected from alkyl, aryl and alkoxy, where R14 and R15 are each selected from alkyl, aryl and alkoxy, where R16 is selected from alkyl groups, and where "n1" is selected such that the siloxane resin has an average molecular weight from about 500 to 5,000. It is desirable that each of the groups R13, R14, R15, and R16 contain less than about six carbon atoms, which, when it comes to R13 and R16, minimizes the hindrance effect and facilitates hydrolysis and condensation reactions in which, when it comes to R14 and R15, relatively volatile alcohols are formed. .
Preferred alkoxy-functional silicone intermediates for the preparation of hydroxy- or epoxy-functional halogenated polysiloxane resins are the alkylalkoxy siloxanes. A particularly preferred alkylalkoxy siloxane is one in which R13 is methoxy, R14, R15 and R16 are each methyl groups. A particularly preferred methylmethoxy siloxane is available e.g. from Wacker Silicones a product called Silres MSE-100 (containing a methoxy function siloxane methyl ester).
The alkylalkoxy siloxane is useful in the preparation of halogenated acrylic and polyester polysiloxane resin compositions as it increases the hardness of the final cured composition. The alkylalkoxy siloxane can optionally be used to prepare halogenated polysiloxane resin compositions in which the hydroxy-functional or alkoxy-functional resin is an epoxy or phenolic resin to further improve chemical and weather resistance and the hydrophobicity of the final composition. It is understood that the alkylalkoxy siloxane component may be used alone or in combination with one or more hydroxyl-functional silicone intermediates and other alkoxy-functional silicone intermediates described above. In a preferred embodiment, up to about 25 weight percent of the alkylalkoxy siloxane component is used for the halogenated polysiloxane resin composition of the present invention based on the total weight of the composition, and more preferably up to about 20 weight percent of the alkylalkoxy siloxane component.
It is further understood that the total amount of silicone intermediates used in the preparation of the halogenated polysiloxane resin compositions of the present invention ranges from about 10 to 70 weight percent based on the total weight of the composition, and more preferably from about 10 to 50 weight percent.
With respect to the resin having a hydroxyl or epoxy function, suitable components with a hydroxyl function are carbinols selected from the group consisting of acrylic resins, polyester resins, phenolic resins, phenol silane resins, and mixtures thereof.
Suitable carbinols are partially esterified or otherwise modified carbinols containing at least two free hydroxyl groups per molecule to facilitate precipitation during polymerization reactions with the silicon-containing component (s) of the invention. Other hydroxyl-containing materials may also be present, which may or may not react with selected silicon components or the silicone intermediate. Thus, the carbinolsilane reaction mixture may contain a monohydroxy reagent such as an alkanol or the like, and such monohydroxy material may be mixed with the carbinol, silane or silicone intermediate at the time it is formed or thereafter.
PL 193 083 B1
The polyol or monohydroxy compound materials have average molecular weights of up to about 10,000 or greater, particularly when they are polyoxalkyl carbinols such as polyoxalkyl glycols or alkyl-containing polyalkoxysilane polyols. The lowest possible molecular weight for the polyol is a weight of about 62, i.e. the molecular weight of ethylene glycol. The higher molecular weight polyols typically make up a lower molar amount of the total carbinol used since the major amount is the lower molecular weight carbinol.
Suitable carbinols are ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, trimethyl propanol, 1,6- or 2,6-hexanediol, neopentyl glycol, 1,3-butylene glycol , pentaerythritol, hexylene glycol, partially esterified polyols, cyclopentanediol, polytrimethylene glycol ether (average molecular weight "WAMW" 650-2900), polypropylene glycol ether (WAMW 400-4000), castor oil and castor oil derivative (WAMW 300-1000), polycaprolaton glycols (WAMW 3002000), polybutadienes terminated with hydroxyl group (WAMW 500-2000), bisphenol A-polyols with hydroxyl function and polycarbonate glycols (WAMW 500-2500), polybutylene ether glycols (WAMW 400-4000), polyoxyethylene propylene glycol ether copolymer (WAMW 400-4000), etc. Mixtures of these polyols can also be reacted, especially when ethylene glycol, propylene glycol or glycerin are present as the main component.
Preferred carbinols include hydroxyl functional acrylic, alkyl or polyester resins or carboxyl functional acrylic, epoxy or polyester resins. Particularly preferred carbinols are acrylic and polyester resins with weight equivalents ranging from about 200 to 1000, with average molecular weights as high as about 10,000. Examples of commercially available carbinols from various sources are acryloid acrylic resins from Rohm and Haas of Philadelphia, PA .; "CDX-500, 586, 581, 587, 611, 678, etc. series of acrylic resins. Of SC Johnson & Sons, Inc. Racine, WI; polyester resins available from Miles, Inc., of Pittsburgh, PA, sold under the product name Desmophen 651, 800, 1100, 1300, 1700, etc. Polyester resins are also commercially available from Cargill, Witco under the product names 5789, 5776 and 5782, and from Rueo Polymer Corparation under the product names S-105, F-2300 and F-2310.
These carbinols are selected to achieve the desired properties in the finally cured composition and because of the lower cost of the compositions containing them compared to compositions composed only of silanes and silicone intermediates. The advantage of carbinols is that they increase the adhesion of a filler or coating to certain substrates or change the mechanical properties of the finally cured composition. Overall, the high molecular weight carbinol has good impact strength and flexibility. Carbinols with a high content of hydroxyl functions are less mobile but exhibit excellent chemical resistance. Acrylic or polyester carbinols show better resistance to ultraviolet light and weathering than bisphenol A or polycarbonate carbinols.
Suitable phenolic resins useful in the preparation of the halogenated polysiloxane resin compositions of the present invention include resins selected from the group consisting of modified and unmodified resoles and novolaks. The phenol resin may already be in polymeric form such as phenol resole and novolac resins or may be formed in situ when all ingredients are combined by mixing phenol or a substituted phenol with an aldehyde in the presence of a strong acid to form phenol novolac or in the presence of a strong base to form phenol resole. The use of phenolic resin is desirable to obtain a halogenated resin composition with enhanced temperature and flame resistance for coatings, composites, adhesives or other such applications.
It has been found that the most useful phenol novolacs for the preparation of halogenated resin compositions are those having an average molecular weight in the range of about 400 to 5000. Useful phenol resoles are those with an average molecular weight in the range of about 300 to 3000. Such phenolic resins are available from trade e.g. with BP Chemical Division of British Petroleum of Barry, UK; the Packaging and Industrial Products Division of Borden, Inc., of Columbus, Ohio, the Durez Division of Occidental Petroleum of Dallas, Texas; Georgia-Pacific Corporation of Atlanta, Georgia; and Neste Resins Corporation of Eugene, Oregon. Preferred phenolic resins include J2018L and 32027L from BP Chemical Cellabond; phenol resole SL-898 from Bordon; and GP5018 phenol resole from Georgia-Pacific.
PL 193 083 B1
Examples of epoxy functional resins useful in the preparation of the halogenated resin compositions of the present invention are epoxy resins containing more than one, and preferably two, 1,2-epoxy groups per molecule. Epoxy resins containing more than two 1,2-epoxy groups per molecule are useful where more favorable chemical and corrosion resistance is desired. Preferably, the epoxy resins are liquids rather than solids and have an epoxy equivalent weight from about 100 to about 500, and have a reactivity of about two. Non-aromatic epoxy resins are useful in these applications where good resistance to ultraviolet light and various weathering conditions is desired.
Preferred epoxy resins are non-aromatic hydrogenated cyclohexane dimethanol and epoxy diglycide ethers with hydrogenated bisphenol A, such as Eponex 1510, Heloxy 107, and Eponex 1513 (bisphenol A-epichlorohydrin hydrogenated epoxy resin) from Texas Holinkin, Texas Holinkin Holink from Monsanto of Springfield, Massachusetts; Epodil 757 (cyclohexane dimethanol diglycidyl ether) from Air Products and Chemicals, Inc., of Allentown, Pennsylvania; Aralditc XUGY358 and PY327 from Ciba Specialty Chemicals of Hawthorne, New York; Epirez 505 from Shell Chemical Company of Louisville, Kentucky; Aroflint 393 and 607 ex Reichllold of Pensacola, Florida; and ERL4221 from Union Carbide of Tarrytown, New York. Other suitable non-aromatic epoxy resins include DER 732 and DER 736 available from the Dow Chemical Company.
In a preferred embodiment, from 10 to 70 weight percent (based on the total weight of the composition) of the hydroxyl or alkoxy functional resin component is used to form the halogenated polysiloxane resin compositions of the present invention. More preferably, from about 10 to 25 weight percent of the hydroxyl or alkoxy functional resin component is used. If a hydroxy or alkoxy functional resin component is taken in an amount outside this range, the resulting halogenated polysiloxane resin composition may not exhibit the desired physical and chemical properties required for specific applications. For example if less than about ten weight percent of the hydroxy functional resin is used, the resulting halogenated resin composition will exhibit reduced ultraviolet light and weathering resistance. If less than about ten weight percent of the epoxy-functional resin is used, the resulting halogenated resin composition will have reduced flexibility and impact resistance. If less than about ten weight percent of the phenolic resin is used, the resulting halogenated resin composition will exhibit reduced heat and flame resistance. When using greater than about 70 weight percent of a resin containing a hydroxyl or epoxy function, it is imperative to reduce the amount of the other silicon-containing components to obtain a halogenated polysiloxane resin composition that can exhibit reduced chemical and corrosion resistance, reduced tack, abrasion resistance, impact resistance, and flexibility.
Concerning halogen-containing organic components, suitable compounds are fluorinated, chlorinated and brominated compounds containing reactive hydroxyl, amino or carboxyl groups, ie having a hydroxyl, amine or carboxyl function. It is important to note that the term "organic" when used to describe the halogen-containing component excludes from the group of halogen-containing components used in the preparation of the halogenated resin compositions of the present invention, inorganic halogen acids. The use of halogenated inorganic acids is deliberately avoided; they are not used in the preparation of the polysiloxane resin compositions of the invention. Halogenated organic compounds with a hydroxyl function are preferred because the Si-OC bond formed during polymerization is more stable than the CN-Si bond produced when the amine function is present.
Preferred halogenated organic compounds containing a hydroxyl functional group are fluoroalcohols, chloroalcohols and bromoalcohols. Fluaralcohols are particularly preferred as they provide increased resistance to ultraviolet light and increased hydrophobicity of the final composition. Preferred fluoroalcohols contain from about one to ten carbon atoms to facilitate polycondensation and allow insertion into the silicone backbone.
Suitable fluoroalcohols include trifluoroethanol, difluoroethanol, hexafluoropropanol, heptafluorobutanol, heptafluoropentanol, hexafluoroisopropanol, methyltrifluorobutanol, octafluoropentanol, perfluorodecanol, 2,2-difluoroethanol, 3H-1H, 4-dodecafluoroethanol, 7 5,5-hepPL 193 083 B1 tafluoro-2-pentanol, 2,2,3,4,4,4-hexafluorobutan-1-ol, hexafluoroisopropanol, hexafluoro-2-methylisopropanol, 2-methyl-4,4,4- trifluorobutanol, 1H, 1H, 5H-octafluoro-1-pentanol, 1H, 1H-pentafluoropropanol-1,1,1,1,3,3,3-hexafluoropropanol, perfluoro-tert-butanol, 1H, 1H, 2H-perfluorodecanol, 1H, 1H-perfluoro-1-heptanol, 1H, 1H-heptafluoro-1-butanol, 2,2,3,3-tetrafluoro-1-propanol, 2,2,2-trifluroethanol, 1,1,1-trifluoro-2-octanol, 1,1,1- trifluoropropanol-2, 3,3,3-trifluoropropanol-1. Preferred fluoroalcohols are commercially available e.g. from 3M Chemical Co., St. Paul, Minn. Under the products L-9704 and FC-10; and from Dupont Chemical of Wilmington, Del. under the product name Zonyl BA-L.
A particularly preferred fluoroalcohol is 2,2,2-trifluoroethanol due to its low price and availability, and also efficiency in the insertion of fluoro groups.
Suitable chloroalcohols include compounds selected from, but not limited to, 1,1,1-trichloroethanol, 2,2,2-trichloroethanol, 2,2-dihydroxy-3,3,3-trichloropropionic acid, and 1,1. , 1-trichloro-2-methyl 2-propanol.
The use of chloroalcohols is desirable in those applications where improved hydrophobicity, chemical resistance and flame resistance are essential.
Suitable bromo alcohols include compounds selected from, but not limited to, 2,3-dibromopropionic acid, 2,3-dibromopropanol, 1,4-dibromo 2,3-butanediol, and 2,3-dibromo 1,4-butanediol . The use of bromo alcohols is appropriate in these applications where increased flame resistance is desired.
The halogen-containing organic component is used to introduce one or more halogen atoms into the polysiloxane polymer formed during the hydrolysis and / or polycondensation of the silicone intermediates (intermediates) and the silane. A preferred halogenated polysiloxane resin composition is prepared by employing the halogenated organic component in an amount ranging from 5 to 25 weight percent based on the total weight of the composition. The use of less than about five weight percent of the halogenated component can result in a halogenated resin composition having poorer properties in chemical resistance, abrasion, flame and weather resistance, and hydrophobicity. By using greater than about 25 weight percent of the halogenated component, a halogenated resin composition can be obtained that is either too hard or too soft for practical use in certain applications, and a resin composition that cures poorly and has poor adhesion.
With regard to the amine hardener, suitable compounds useful to facilitate the course of the hydrolysis and / or polycondensation reaction of the silicone intermediate and / or the hydroxylated and epoxidized resin include amines selected from the main classes of aliphatic amines, aliphatic amine adducts, polyamidoamines, cycloaliphatic amines and cycloaliphatic amine adducts, amines aromatics, Mannich bases and ketimines which may be substituted wholly or partially with the aminosilane. Preferred amine hardeners are the amino silanes of the general formula
Y-Si- (OX) 3 where Y is H (HNR17) a and "a is an integer from two to seven, where each R17 is a difunctional organic radical independently selected from the group consisting of aryl, alkyl, dialkylaryl, alkoxyalkyl and cycloalkyl, and R17 may vary for each Y molecule, and wherein each X may be the same or different, and is limited to alkyl, hydroxyalkyl, alkoxyalkyl, and hydroxyalkoxyalkyl groups having less than about six carbon atoms. More than one aminosilane may be used if desired to prepare the halogenated polysiloxane resin compositions of the present invention.
Preferred, but not limited to, aminosilanes are: aminoethylaminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, n-phenylamino-propyltrimethoxysilane, trimethoxysilylpropyl diethylene triamine, 3- (3-aminophenoxy) propyltrimethoxy-methylphenylsilane, 3- (3-aminophenoxy) propyl trimethoxy-methylphenylsilane, 3-aminophenoxy) propyl-trimethoxy-methylphenylsilane, aminoethylaminopropyltrimethoxysilane, n-aminohexyl aminopropyl trimethoxy silane and tris aminopropyl trismethoxy ethoxy silane.
Table 1 lists the manufacturers and trade names of certain aminosilanes useful in the present invention
PL 193 083 B1
TABLE 1 - Aminosilanes
<td>Manufacturer</td><td>Manufacturer's designation</td>
<td>Dow Corning</td><td>Z6020, XI-6100, XI6150</td>
<td>Union Carbide</td><td>A1100, A1101, A1102, A1108, A1110, A1120, A1126, A1130, A1387, Y9632</td>
<td>Wacker</td><td>ED117</td>
<td>H ^ s</td><td>A0696, A0698, A0699, A0700, A0710, A0720, A0733, A0733, A0742, A0750, A0800</td>
<td>PCR</td><td> 12328-1</td>
The halogenated polysiloxane resin composition is prepared using up to about 20 weight percent amine hardener based on the total weight of the composition, and more preferably up to about 12 weight percent amine hardener. A halogenated resin composition made with greater than about 20 weight percent of the amine hardener can result in resin compositions that are highly cross-linked and thus exhibit poor impact resistance, flexibility, weathering, and shelf life.
Another class of compounds useful as catalysts for facilitating the course of the hydrolysis and polycondensation reactions and thereby reducing reaction times and the use of elevated temperatures are compounds selected from the group consisting of organometallic compounds, acids, bases, and mixtures thereof. More than one type of organometallic catalyst may be used as required. Useful organometallic compounds are metal dryers well known in the dye industry such as zinc, manganese, cobalt, iron, caprylates, lead and tin neodecanoates and naphthenates, etc. Organotitanates such as butyl titanate and the like are also useful for the present invention.
Organometallic compounds useful as catalysts in the preparation of halogenated resin compositions include those of the general formula <sup>R</sup>l \ <sup>R</sup>19 / S \ <sup>R</sup>20 <sup>R</sup>21 wherein R18, R19, R20 and R21 are groups selected from alkyl, aryl, aryloxy and alkoxy of up to 11 carbon atoms, and where any two of R18, R19, R20 and R21 are further selected from inorganic atoms such as halogen, sulfur and oxygen.
Example organotin compounds include tetramethyltin, tetrabutyltin, tetraoktylocyna, tributyltin chloride, tributyltin methacrylate, dichorek dibutyltin oxide dibutylcyny sulfide, dibutyltin acetate, dibutyltin dilaurate dibutylocyn polymer maleate, dibutyltin dilaurylomerkaptyd dibutyltin octoate, tin bis (isooctylthioglycolate), dibutyltin trichloride, butyltin butylcinic acid, dioctyltin dichloride, dioctyltin oxide, dioctyltin dilaurate, a polymer of dioctyltin maleate, dioctyltin bis (isooctylthioglycolate), dioctyltin sulfide, dibutyltin diacetylacetonate, and dibutyltin 3-mercaptopropionate. Preferred organometallic compounds are commercially available from, e.g., Nitto Kasei Co. Ltd under the product name U-220; from QSI Specialties under the product name NIAX Catalyst U-220 (Dibutyldiacetyltin acetonate); and with Air Products and Chemicals. Inc. Under the product name METACURE T-1.
Halogenated polysiloxane resin compositions are prepared using up to about ten percent by weight of the organometallic catalyst based on the total weight of the composition, and more preferably up to about four percent by weight of the organometallic catalyst. A halogenated polysiloxane resin composition made with greater than about ten percent by weight of the organometallic catalyst may result in a composition with greater flexibility than expected here. While it should be understood that the use of an amine hardener and an organometallic catalyst is preferred, the preferred embodiments of the preparation of halogenated polysiloxane resin compositions employ both the aminosilane and organometallic catalyst components in amounts for each previously described.
If necessary, one or more organic solvents are used to dissolve other organic components, which facilitates the course of the hydrolysis and polycondensation reactions and this facilitates the control of film thickness and coating with the composition. Preferred solvents include volatile solvents with a relatively low VOC content which allows rapid drying of halogenated resin compositions when being coated as coatings. Examples of solvents that can be used are oxygen containing solvents such as esters, ethers, alcohols, ketones, glycols, and aromatic solvents such as toluene, xylene, etc.
Specific solvents are e.g. MIBIC, MEK, acetone, n-propyl ketone, methyl isoamyl ketone, methyl propyl ketone, isopropanol, isobutyl alcohol, n-butyl alcohol, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, triethylamine, n-butyl acetate , Ethyl 3-ethoxypropionate, pentanone, etc.
The halogenated resin composition may contain up to about ten percent by weight of a solvent.
The halogenated polysiloxane resin compositions of the present invention may also contain conventional fillers such as silica powder, talc (magnesium silicate), clays such as white clay (aluminum silicates), wollastonite (calcium silicate), calcium carbonate, barites (barium sulfate, barium metaborate) , aluminum trihydrate, alumina, graphite, zinc, aluminum, copper, mica, lamellar ferric oxide, aluminum flakes, calcined aluminum oxide, glass flakes, and stainless steel flakes.
Pigments such as iron oxide, alumina, titanium dioxide, and chrome yellow can also be used. Pigments containing lead should be avoided as it interacts with the hardener. Organic pigments such as Hansa Yellow, Phthalic Green and Phthalate Blue are used to color the product. Zinc oxide can be used as a film hardener. Barium metaborate is the preferred filler for acid resistance; it has been found that coating compositions containing barium metaborate show enhanced resistance to acids.
Finely divided pigment or filler particles must be used when a composition is desired to be resistant to high temperatures. Examples of such fillers that show resistance to high temperatures are barite (barium sulfate), mica, lamellar ferric oxide, alumina flakes, alumina, calcined alumina, glass flakes, stainless steel flakes, etc. By proper selection of filler and binder, heat-resistant coatings that are resistant to temperatures in excess of 1000 ° F are obtained.
Other commonly used materials and additives are plasticizers, adhesion promoters, flow additives, pigment dispersion wetting agents and thixotropic agents such as silicon foam. For example, a catalytic amount, up to about one weight percent of the total weight of the composition, of an adhesion promoter is added to improve the adhesion of the composition to the coated material. Up to about 50 weight percent, based on the total weight of the composition, such as fillers, pigments, materials, and additives may be added as required.
Exemplary halogenated acrylic and polyester polysiloxane resin compositions of the present invention are prepared by combining together a silicone intermediate, an optional aralkoxy silane, an optional organometallic catalyst, and an optional amine hardener to form a first mixture and heating the mixture for a period of time. An optional alkylalkoxy silane, an optional second arylalkoxy silane, and a second silicone intermediate are added to the first mixture to form a second mixture which is heated. A third and fourth silicone intermediates, an organic solvent, a halogen-containing alcohol, an acrylic or polyester resin and an optional second organometallic catalyst are added to the second mixture to obtain the final product.
Exemplary halogenated polysiloxane epoxy and phenolic resin compositions of the present invention are prepared by combining a halogen-containing organic component, a silicone intermediate, an optional organometallic catalyst to form a first mixture and heating it for a period of time. An optional arylalkoxy silane, a second silicone intermediate, and an epoxy or phenolic resin are added to the first mixture to form a second mixture which is cooled to the desired temperature. An optional second organometallic catalyst and an optional aminosilane are added to the second mixture and mixed until a homogeneous final product is obtained.
PL 193 083 B1
In exemplary embodiments, the resulting halogenated polysiloxane resin compositions are stored in individual containers and are sold as a single product. Before use, the container is opened and the composition then finally cures under the influence of atmospheric moisture. Moisture in the presence of a catalyst brings the hydrolysis and polycondensation reactions to completion. Alternatively, the halogenated resin compositions of the present invention are prepared as a two-component system by providing some or a portion of the hardeners and catalysts in a second container, the contents of which are mixed with the contents of the first container before use.
Without wishing to be bound by any particular theory or mechanism, it is believed that the halogenated hydroxyl functional polysiloxane resin compositions of the present invention are formed as follows. After the components are combined, the silicone intermediates undergo controlled gradual hydrolysis, and the optional silane, hydrolyzed silicone intermediates and the hydroxyl-functional halogenated component undergo polycondensation reactions to form a halogenated organoxysilane containing residual silanol groups. During the polycondensation reaction, the optional silane and the hydrolyzed silicone intermediates also condense together to form a cross-linked polysiloxane system. During the polycondensation reaction, the hydroxyl-functional resin condenses with itself to form a polymeric resin, and condenses with the silanol groups of the halogenated organoxysilane, thereby introducing the resin into the halogenated polysiloxane network to form a halogenated polysiloxane resin composition.
The halogenated epoxy functional polysiloxane resin compositions of the present invention are also believed to be prepared as follows. As with the hydroxyl-functional polysiloxane resin compositions described above, when the components are combined, the silicone intermediates undergo a controlled gradual hydrolysis, and the optional silane, hydrolyzed silicone intermediates, and hydroxyl-functional halogenated components undergo polycondensation reactions to form a halogenated organoxysilane containing residual silanol groups. During the polycondensation reaction, the optional silane and the hydrolyzed silicone intermediates also condense together to form a cross-linked polysiloxane system.
During the polycondensation reaction, the epoxy component reacts with an optional aminosilane hardener to form a cured polymeric epoxy resin with an attached alkoxy group (function). The alkoxy function of the epoxy resin is hydrolyzed by water and condensed with the silanol groups of the halogenated organoxysilane, thereby introducing the resin into the halogenated polysiloxane network and producing a halogenated polysiloxane resin composition.
The essence of the present invention is that it allows the resin to be halogenated without the need of using halogen-containing inorganic acids such as hydrofluoric acid and the like by reacting the resin with the condensation product of a halogen-containing organic compound and hydroxyl, amine or carboxyl functional groups and organooxysilane.
The following examples are presented to illustrate various embodiments of the halogenated polysiloxane resin compositions prepared according to the present invention.
Example No. 1 - Fluorinated acrylic polysiloxane resin composition
The fluorinated acrylic polysiloxane resin composition is prepared by combining approximately 100 g of an alkylalkoxy siloxane (Silres MSE 100), 20 g of a first arylalkoxy silane (Z-6124), 4 g of an organometallic catalyst (NIAX U-220), and 15 g of an aminosilane (Z6020) to form first mixture.
The first mixture is heated to about 150 ° F and stirred for about 30 minutes. Each of the ingredients is added to the first mixture: about 50 g of the alkylalkoxy silane (A-163 and Z6070), 80 g of a second arylalkoxy silane (SY-201), 150 g of the first alkoxy-functional silicone intermediate (DC3074 and SY-231) and all of this. is refluxed for about one hour at about 180 ° F.
About 25 g of a second alkoxy functional silicone intermediate (DC6-223D), 25 g of a first organic solvent (PM Acetate) and 15 g of a second organic solvent (butyl acetate) are slowly added to the boiling mixture. About 160 g of acrylic resin (CDK-588), 35 g of hydroxyl-functional silicone intermediate (QI-2530), 80 g of 2,2,2-trifluoroethanol and 2 g of organometallic catalyst are added to the mixture and the mixture is heated to reflux temperature. reflux for about two hours at about 180 ° F. About 435 g of a white pigment and 30 g of a first organic solvent are added to the heated mixture to obtain a white fluorinated acrylic polysiloxane resin composition.
Example No. 1A - Fluorinated acrylic polysiloxane resin composition
The fluorinated acrylic polysiloxane resin composition was prepared as described above in Example 1, except that instead of about 50 g of the alkylalkoxy silane (A-163 and Z6070), 60 g of fluorinated silane (Q3-9030) was used to further improve the abrasion resistance. and weather conditions.
Example No. 2 - Fluorinated acrylic polysiloxane resin composition
The fluorinated acrylic polysiloxane resin composition is prepared by combining approximately 120 g of an alkylalkoxy siloxane (Silres MSE 100), 25 g of a first arylalkoxy silane (Z-6124), 5 g of an organometallic catalyst (NIAX U-220), and 20 g of an aminosilane (Z6020) to form first mixture. The first mixture is heated to about 150 ° F and stirred for about 30 minutes. About 60 g of the alkylalkoxy silane (A-163 and Z6070), 95 g of a second arylalkoxy silane (SY-201) and 180 g of the alkoxylated silicone intermediate (DC3074 and SY-231) are added to the first mixture and heated to reflux. reflux for about one hour at about 180 ° F.
The pre-mixed ingredients are slowly added to the reflux mixture: about 30 g of a second alkoxy-functional silicone intermediate (DC6-2230), 30 g of a first organic solvent (PM Acetate) and 20 g of a second organic solvent (Acetate butyl). About 190 g of acrylic resin (CDX-588), 40 g of hydroxyl functional silicone intermediate (QI-2530), 100 g of 2,2,2-trifluoroethanol and 2 g of organometallic catalyst are added to the mixture and the mixture is heated to reflux temperature. reflux for about two hours at 180 ° F to obtain a clear composition of a fluorinated polysiloxane acrylic resin.
Example No. 2A - Fluorinated acrylic polysiloxane resin composition
The fluorinated acrylic polysiloxane resin composition was prepared as described above in Example 2, except that instead of about 60 g of the alkylalkoxy silane (A-163 and Z6070), 70 g of fluorinated silane (Q3-9030) was used to further improve the toughness. to abrasion and weather conditions.
Example No. 3 - Fluorinated epoxy polysiloxane resin composition
The fluorinated epoxy polysiloxane resin composition is prepared by combining together about 145 g of 2,2,2-trifluoroethanol, 300 g of alkoxy functional silicone intermediate (SY-231), 10 g of the first organometallic catalyst (NIAKU-220), and the mixture is heated to temperature about 180 ° F for one hour. The mixture is cooled to about 120 ° F and about 20 g of an alkylalkoxy silane (A-163 and G6070), 140 g of an alkylalkoxy siloxane (Silres MSE 100), and 200 g of epoxy resin (Eponex 1510) are added. The mixture is agitated until homogeneous and re-cooled to about 120 ° F. About 15 g of a second organometallic catalyst (METACURE T-1) and 100 g of an aminosilane hardener (A1100) are added to the mixture and mixed until uniform and a fluorinated epoxy polysiloxane resin composition is formed.
Example No. 4 - Fluorinated epoxy polysiloxane resin composition
The fluorinated epoxy polysiloxane resin composition is prepared by combining approximately 200 g of 2,2,2-trifluoroethanol, 350 g of the alkoxy functional silicone intermediate (SY-321), 25 g of the alkylalkoxy silane (A-163 and Z607D), 200 g of epoxy resin (Eponex 1510); the ingredients are mixed until uniform and the mixture is cooled to about 120 ° F. About 10 g of organometallic catalyst (METACURE T-1) and 80 g of an aminosilane (A1100) are added to the mixture and mixed until homogeneous to form a fluorinated epoxy polysiloxane resin composition.
Example No. 5 - Fluorinated epoxy polysiloxane resin composition
The fluorinated epoxy polysiloxane resin composition is prepared by combining approximately 200 g of hexafluoropropanol, 350 g of the alkoxy functional silicone intermediate (SY-231), 25 g of the alkylalkoxy silane (A-163 and Z6070), 200 g of epoxy resin (Eponex 1510), and the ingredients are mixed until homogeneous, then the mixture is cooled to about 120 ° F and about 10 g of organometallic catalyst (METACURE T-1) and 80 g of aminosilane are added to the mixture
(A1100) and mixed until uniform and a fluorinated epoxy polysiloxane resin composition was formed.
Example No. 6 - Chlorinated epoxy polysiloxane resin composition
The chlorinated epoxy polysiloxane resin composition is prepared by combining about 145 g of trichloroethanol, 400 g of the alkoxy functional silicone intermediate (SY-231), 20 g of an alkylalkoxy silane (A-163 and 26070), 200 g of epoxy resin (Eponex 1510); the ingredients are mixed until uniform and the mixture is cooled to about 120 ° F. About 10 g of organometallic catalyst (METACURE T-1) and 80 g of an aminosilane (A1100) are added to the mixture and mixed until homogeneous to form a chlorinated epoxy polysiloxane resin composition.
Example No. 7 - Fluorinated epoxy polysiloxane resin composition
The fluorinated epoxy polysiloxane resin composition is prepared by combining approximately 190 g of fluoroalcohol (Zonyl BA-L), 350 g of alkoxy-functional silicone intermediate (SY-231), 20 g of alkylalkoxy silane (A-163 and Z6070), 200 g of epoxy resin (Eponex 1510 ); the ingredients are mixed until uniform and the mixture is cooled to about 120 ° F. About 10 g of organometallic catalyst (METACURE T-1) and 80 g of an aminosilane (A1100) are added to the mixture and mixed until homogeneous to form a fluorinated epoxy polysiloxane resin composition.
Example No. 8 - Fluorinated epoxy polysiloxane resin composition
The fluorinated epoxy polysiloxane resin composition is prepared by combining approximately 200 g of heptafluoropropanol, 350 g of the alkoxy functional silicone intermediate (SY-231), 20 g of an alkylalkoxy silane (A-163 and Z6070), 200 g of epoxy resin (Eponex 1510), and the ingredients are mixed until uniform, then cool the mixture to about 120 ° F. About 10 g of organometallic catalyst (METACURE T-1) and 80 g of an aminosilane (A1100) are added to the mixture and the mixture is mixed until homogeneous.
From the crude compositions of Examples 3-8, wet layers approximately eight millimeters thick were prepared on the Bonderite 1000 stainless steel panels and allowed to cure for approximately seven days at 77 ° F and 50 percent relative humidity prior to testing. The compositions of each Example showed dry to the touch in less than about 10 hours, and half of them in less than about 7 hours. The compositions of the examples are tested for chemical resistance by exposure to various acids and bases. The compositions of Examples 3-6 and 8 showed excellent chemical resistance. The compositions of the examples were also tested for weather resistance by measuring 63 percent gloss retention after exposure of the compositions (drawn down) to ultraviolet light for up to 24 weeks. Examples 3-6 and 8 showed excellent gloss retention with QUV-accelerated exposure for up to about 8 weeks.
The halogenated polysiloxane resin compositions prepared according to the present invention exhibited excellent chemical, corrosion, weathering and ultraviolet light resistance properties compared to halogenated resin compositions prepared by conventional halogen acid-based methods. For example when specular gloss was measured in accordance with ASTM D 523 using a 60 ° gloss meter, the cured fluorinated polysiloxane acrylic resin compositions prepared according to Example No. 1 of this invention exhibited a much better initial specular gloss and specular gloss within 85 days compared to fluoride polyvinylidene "PVDF".
Specifically, the composition of Example No. 1 of the present invention has an initial specular gloss value of about 80 (high gloss) compared to a value of about 38 (medium gloss) for PVDF. Accordingly, the composition of Example No. 1 exhibited a specular gloss that was twice as good as that of the PVDF product. After about 20 days, Example No. 1 had a specular gloss value of about 72 and a percent gloss retention of 92 percent, while the PVDF product had a specular gloss value of about 32 and a percent gloss retention of about 94 percent.
After about 48 days, the Example No. 1 composition had a specular gloss value of about 70 and a gloss retention of 90 percent, while the PVDF product had a specular gloss value of about 28 and a gloss retention of about 90 percent. After about 85 days, the Example No. 1 composition had a specular gloss value of about 68 and a gloss percent retention of 88 percent, while the PVDF product had a specular gloss value of about 28.
PL 193 083 B1 and percent gloss retention of about 90 percent. Thus, after 85 days, the Example No. 1 composition had a specular gloss value nearly two and a half times that of the PVDF product.
The specular gloss test illustrates that the halogenated polysiloxane resin compositions of the present invention exhibit superior gloss properties compared to conventional halogenated compositions and retain these superior properties over a long period of time much better than conventional compositions. The improved gloss retention is due to the enhanced weather and ultraviolet light resistance of the halogenated polysiloxane resin compositions of the present invention.
Table 2 summarizes the data collected from the comparative tests performed according to AAMA 605.2 standards with the compositions of Examples Nos. 1 and 1A and the PVDF product. These tests illustrate that coatings made from halogenated polysiloxane resin compositions prepared in accordance with the principles of the present invention (Examples Nos. 1 and 1A) exhibit improved specular gloss properties, improved abrasion resistance, more moisture resistance, and improved gloss retention compared to coatings produced by from the PVDF product.
TABLE 2 - Results of various tests
<td>Test</td><td>AAMA 605.2</td><td>The results of examples 1 and 1A</td><td>Results for the PVDF product</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td>
<td>Color uniformity</td><td> 7.1</td><td>Color uniformity in the range</td><td>Color uniformity in the range</td>
<td>Specular gloss</td><td> 7.2</td><td>60 degrees, gloss = 76</td><td>60 degrees, gloss = 32</td>
<td>Dry hardness movie</td><td> 7.3</td><td>No film cracks at F degree</td><td>No film cracks at F degree</td>
<td>Film adhesion</td><td> 7.4.1.1</td><td>Dry adhesion Not removing the film</td><td>Dry adhesion Not removing the film</td>
<td>Film adhesion</td><td> 7.4.1.2</td><td>Morka adhesion Not removing the film</td><td>Wet adhesion Not removing the film</td>
<td>Film adhesion</td><td> 7.4.1.3</td><td>Adhesion in boiling water Not removing the film</td><td>Adhesion in boiling water Not removing the film</td>
<td>Impact resistance</td><td> 7.5</td><td>Non-removal of the film with minimal deformation 0.1 +/- 0.01</td><td>Non-removal of the film with minimal deformation 0.1 +/- 0.01</td>
<td>Abrasion resistance</td><td> 7.6</td><td>Abrasion coefficient> 40, actual</td><td>Abrasion coefficient> 40, actual = 70-80</td>
<td>Chemical resistance</td><td> 7.7.1</td><td>Acid resistance salt. 15 minute spot test. No blisters or visual changes</td><td>Hydrochloric acid resistance. 15 minute spot test. No blisters or visual changes</td>
<td>Chemical resistance</td><td> 7.7.2</td><td>Mortar resistance (24 hour test)</td><td>Mortar resistance (test 24 hours)</td>
<td>Resistance to acid pollutants</td><td> 7.7.3</td><td>Color change should be less than 5E units (current results = = 0.5)</td><td>Color change should be less than 5E units (current results = = 0.4)</td>
<td>Resistance to detergents</td><td> 7.7.4</td><td>No loss of adhesion; no bubbles</td><td>No loss of adhesion; no bubbles</td>
<td>Corrosion resistance</td><td> 7.8.1</td><td>Moisture resistance. No more than a few 8F bubbles per 3000 hours in a humidity chamber</td><td>Moisture resistance. 8D and 6-5F bubbles after 3000 h in a Cleveland humidity chamber (ASTMD2247)</td>
PL 193 083 B1 cont. table 2
<td> 1</td><td> 2</td><td> 3</td><td> 4</td>
<td>Corrosion resistance</td><td> 7.8.2</td><td>Salt spray resistant. 3000 hours in a tray spray booth (ASTM B117). Meets minimum scratch values 7 and minimum bubble values 8</td><td>Salt spray resistant. 3000 hours in a tray spray booth (ASTM B117). Meets minimum scratch values 7 and minimum values blisters 8</td>
<td>Resistance has weather conditions</td><td> 7.9.1</td><td>the EMMAQUA-NTM test was carried out in DSET laboratories. Pho- enix, Arizona according to the standard ASTM U4141-93 Procedure C: Onset of Exposure - 9/9/95; end 10/10/96; Total Radial Exposure (MJ / m2) - 5,551,735; Total exposure radial (lys) -13268997; UV radiation exposure (MJ / m2) - 1400; Daily exposure - 368; Delta E-0.82</td><td>the EMMAQUA-NTM test was carried out in DSET laboratories. Pho- enix, Arizona in line with ASTM U4141-93, Procedure C: Onset of exposure -9/9/95; end 10/10/96; Total Radial Exposure (MJ / m2) -5551735; Total Radial Exposure (lys) 13,268,997; UV radiation exposure (MJ / m2) -1400; Daily exposure - 368; Delta E-0.82</td>
The halogenated polysiloxane resin compositions of the present invention can be applied to many materials (substrates) such as steel, masonry, plastic, etc., cured at ambient temperature without the need for special conditions or equipment. The compositions cure rapidly, completely at ambient temperature and greater than fifty percent humidity in less than about 10 hours, and can be applied with fabric, spraying, brush or roller without the need for dilution or special techniques and equipment.
The halogenated polysiloxane resin compositions of the present invention can be used, in addition to providing protective coatings, to construct composites such as fiber-reinforced plastics in the form of templates, profiles, etc. used in automobiles, freight transport, buildings and structures, airspace and defense, and in the mining and mining industries. boring tunnels providing increased flexibility, impact resistance and hardness. Specific examples of such composites are pipes (10) having reinforcing fibers or filaments as shown in the accompanying drawing. Such pipes are made from coils of filaments made of glass, aromatic Kevlar polyamide, carbon, graphite and the like, or combinations thereof, bonded together with the halogenated polysiloxane resin composition of the present invention.
While only a limited number of embodiments of halogenated polysiloxane resin compositions are given herein, many modifications and variants will be apparent to those skilled in the art. Accordingly, it is to be understood that, within the scope of the appended claims, the halogenated polysiloxane resin compositions of the present invention may be prepared other than as specifically described herein.
Contents5
4 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4
29 members in 17 offices
Priority claims5
| Document | Office | Kind | Date |
|---|---|---|---|
| 86879397 | United States of America | A | |
| 9810421 | United States of America | W | |
| 08868793 | – | – | – |
| US19970868793 | – | – | – |
| WO1998US10421 | – | – | – |
Members29
| Document | Office | Kind | |
|---|---|---|---|
| CA2293776A1 | Canada | A1 | |
| WO9855056A1 | World Intellectual Property Organization (WIPO) | A1 | |
| AU7500698A | Australia | A | |
| NO995903D0 | Norway | D0 | |
| US6013752A | United States of America | A | |
| NO995903L | Norway | L | |
| WO9855056A8 | World Intellectual Property Organization (WIPO) | A8 | |
| EP0986352A1 | European Patent Office (EPO) | A1 | |
| BR9809961A | Brazil | A | |
| PL337326A1 | Poland | A1 | |
| CN1263453A | China | A | |
| AU734470B2 | Australia | B2 | |
| NZ501592A | New Zealand | A | |
| EP0986352A4 | European Patent Office (EPO) | A4 | |
| JP2002514260A | Japan | A | |
| MY115753A | Malaysia | A | |
| RU2213111C2 | Russian Federation | C2 | |
| TW591082B | Taiwan Province of China | B | |
| EP0986352B1 | European Patent Office (EPO) | B1 | |
| DE69835287D1 | Germany | D1 | |
| EP1716827A2 | European Patent Office (EPO) | A2 | |
| PT986352E | Portugal | E | |
| EP1716827A3 | European Patent Office (EPO) | A3 | |
| PL193083B1This record | Poland | B1 | |
| ES2268775T3 | Spain | T3 | |
| DE69835287T2 | Germany | T2 | |
| CN100355408C | China | C | |
| JP2008150620A | Japan | A | |
| CA2293776C | Canada | C |
1 legal event, as the office reported them to INPADOC
Events
| Event | Code | |
|---|---|---|
| Decisions on the lapse of the protection rightsLapsedLAPS | LAPS |
Numbers
- Publication
- 193083
- Publication, DOCDB
- 193083
- Publication, EPODOC
- PL193083B
- Application
- 378395
- Application, DOCDB
- 37839598
- Application, EPODOC
- PL19980378395
Titles2
- English
- Composition based on halogenated resins
- Polish
- Kompozycja chlorowcowanej żywicy polisiloksanowej oraz sposób wytwarzania kompozycji chlorowcowanej żywicy polisiloksanowej
Classification
- CPC, 2
- C08G77/442
- C08G77/42
- IPC, 10
- C08L83 04
- C08L83 08
- C08G77 24
- C08G77 385
- C08G77 42
- C08G77 442
- C08L83 10
- C08L101 00
- C09D183 04
- C09D183 10
