WO1991011467A1 - Ethers alkenyles et compositions polymerisables par radiation - Google Patents

Ethers alkenyles et compositions polymerisables par radiation Download PDF

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Publication number
WO1991011467A1
WO1991011467A1 PCT/US1990/006758 US9006758W WO9111467A1 WO 1991011467 A1 WO1991011467 A1 WO 1991011467A1 US 9006758 W US9006758 W US 9006758W WO 9111467 A1 WO9111467 A1 WO 9111467A1
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WIPO (PCT)
Prior art keywords
ether
value
mixture
alkyl
chr
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PCT/US1990/006758
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English (en)
Inventor
Fulvio J. Vara
James A. Dougherty
Jeffrey S. Plotkin
Kolazi S. Narayanan
Paul D. Taylor
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Isp Investments Inc.
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Priority claimed from US07/470,487 external-priority patent/US5045572A/en
Priority claimed from US07/470,489 external-priority patent/US5039716A/en
Application filed by Isp Investments Inc. filed Critical Isp Investments Inc.
Publication of WO1991011467A1 publication Critical patent/WO1991011467A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/04—Esters of silicic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4085—Curing agents not provided for by the groups C08G59/42 - C08G59/66 silicon containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

  • X is halogen, -OR wherein R is lower alkyl, a mixture of halogen and -OR, a mixture of -OR and hydrogen or a mixture of halogen and hydrogen;
  • R- ⁇ contains from l to 8 carbon atoms and is alkylene, alkenylene, alkynylene, optionally alkoxylated with up to 20 units of
  • Y is hydrogen or methyl
  • R 2 is hydrogen or lower alkyl
  • n has a value' of from 1 to 4.
  • silicate reactants include tetrachlorosilane, tetrafluorosilane, tetrabromosilane, tetramethyl orthosilicate, tetrabutyl orthosilicate, tetraethyl orthosilicate, tetrapropylyl orthosilicate, diethyl orthosilicate, dipropyl orthosilicate, tributyl orthosilicate, triethyl orthosilicate, tribromoethyl orthosilicate, dichlorodiethyl orthosilicate.
  • hydroxy vinyl ethers which are suitably employed in the reaction include hydroxybutyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl prop-1-enyl ether, hydroxyethyl but-1-enyl ether, hydroxyhexyl vinyl ether, hydroxyethyl 2-butyl hex-1-enyl ether, hydroxy butenyl vinyl ether, hydroxybutynyl vinyl ether, hydroxybutynyl-prop-1-enyl ether, hydroxypropynyl vinyl ether, hydroxybutyl 3-methylprop-l-enyl ether, the vinyl ether of di-hydroxymethyl cyclohexane and alkoxylated vinyl ether derivatives of the above having the formula
  • m has a value of from 1 to 20, preferably from 1 to 8 and R lf Y and R 2 are as defined above.
  • the mole ratio of silicate to hydroxylated alkenyl ether depends on the number of terminal alkenyl groups desired in the product and the number of halo and or OR groups in the silicate reactant and is as close to stoichiometry as is conveniently maintained; although up to a 10:1 excess of silicate reactant over said stoichiometric amount is within the scope of this invention.
  • the reaction is carried out under anhydrous conditions in the presence of from about 0.01 to about 10 wt. %, preferably from about 0.1 to about 5%, of a base catalyst based on the alkenyl ether reactant.
  • Catalysts such as sodium or potassium metals, sodium or potassium hydroxides, hydrides, alkoxides or salts of the hydroxy alkenyl ether as well as titanium alkoxide are suitably employed.
  • halogenated silicates When halogenated silicates are employed, the addition of a base is required during the reaction to neutralize any hydrogen halide which is generated as by-product.
  • Suitable bases include sodium hydroxide, potassium hydroxide, sodium or potassium alkoxides, pyridine or basic pyridine derivatives, ammonia and amines such as trimethyl a ine, tripropylamine and the like.
  • the reaction mixture may also be affected in up to 90%, preferably not more than 50% suitable inert solvent such as toluene benzene, methyl ethyl ketone, N-methyl pyrrolidone, tetrahydrofuran, ethyl acetate, acetonitrile, and the like.
  • suitable inert solvents are those having a boiling point below that of the desired product.
  • the reaction is carried out at a temperature between about 50° and about 200°C. for a period of from about 5 to about- 48 hours under from ambient pressure up to about 500 psi.
  • Preferred reaction parameters include a temperature of between about 100° and about 120°C. , a reaction time of from about 10 to 20 hours and a pressure from atmospheric to about 50 psi.
  • High conversion to product is achieved in the present reaction although a product mixture of mono and poly substituted silicates is usually obtained.
  • Individual products can be separated by fractional distillation if desired. The crude product is separated from base catalyst by usual methods such as extraction and filtration, and from solvent, by evaporation under reduced pressure.
  • a major advantage of the present products is that they are rapidly curable at ambient temperatures by UV and visible light or other sources of radiation such as an electron beam, x-ray, laser emissions and the like. They are also reactive diluents for highly viscous coating materials, such as acrylates, vinyl ethers, epoxides, and non-reactive resins, etc., to promote rapid curing and strong bonding to substrate surfaces. From about 1 to about 60 wt. %, preferably from about 1 to about 30 wt. %, of the present alk-1-enyl ether silicates are added to said acrylates, epoxides and/or vinyl ethers to improve their curing properties.
  • a radiation curable, cross linkable composition containing (a) from about 0.1 to about 5 wt. % of an initiator containing at least 25% of a cationic initiator, (b) from about 0 to about 60 wt. % of one or more polymerizable components of the group of a vinyl ether, epoxide, acrylate or a vinyloxy alkyl urethane and (c) from about 35 to about 99.9% wt. % of an aliphatic polyfunctional alkenyl ether having the formula (II)
  • compositions are those containing between about 20% and about 50% of component (b) and between about 50% and about 80% of component (c) where R is methyl.
  • the present polyfunctional alkenyl, preferably propenyl, ether compounds of Formula (II) are homopolymerizable resins independently useful as protective coatings and are also effective cross-linking agents for polymerizable vinyl ethefs having at least 6 carbon atoms or epoxides such as the divinyl ethers of the bis(hydroxyethyl) ether of bisphenol A, the divinyl ether of triethylene glyc ⁇ l the divinyl ether of dimethylolcyclohexane, vinyloxyalkyl urethanes, e.g.
  • divinyloxybutyl urethane oligomers the diglycidyl ether of bisphenol A and its oligomers, bisphenol A epoxy acrylate and its oligomers, 3,4-eppxycyclohexyl methyl-3 ' ,4'-epoxycyclohexane cairb ⁇ xylate, the ethers disclosed in U.S. patents 4,388,450; 4,749,807; 4,775,732 and 4,751,271 and corresponding alkoxylated compounds and similar comonomers in monomeric or oligomeric form having a number average molecular weight up to about 5,000 or mixtures of said comonomers and/or copolymers.
  • Such monomeric or polymeric vinyl ethers, epoxides, acrylates or urethanes can be reacted with the polyfunctional alkenyl ethers of this invention to form a cross-linked copolymeric product having a high cross-linked density and extremely high resistance to abrasion and chemical attack.
  • the present polyfunctional alkenyl ethers are homopolymerizable forming an exceedingly branched structure.
  • these agents can be used as rigid coatings on substrates which require an exceptionally high strength, resistance to abrasion and solvent attack.
  • Substrates on which the copolymerized or homopolymerized agent is suitably coated include metal, wood, ceramic, plastic, leather, paper, glass and the like.
  • the present composition is coated on the substrate by any convenient and conventional technique in the desired thickness, usually in a thickness of between about 0.1 to about 5 mils.
  • the alkenyl ethers of this invention can be admixed with the above acrylate, urethane, epoxide or vinyl ether monomers or their oligomeric counterparts to effect cross-linking in the presence of a cationic initiator, such as a triphenyl sulfonium salt of phosphorous hexafluoride, diphenyl iodonium salt, a mixture of aromatic complex salts of butyrolactone, a phenyl ; ⁇ nium salt or an aryl alkyl oniu salt, etc.
  • a cationic initiator such as a triphenyl sulfonium salt of phosphorous hexafluoride, diphenyl iodonium salt, a mixture of aromatic complex salts of butyrolactone, a phenyl ; ⁇ nium salt or an aryl alkyl oniu salt, etc.
  • the initiators suitable to effect polymerization reactions of the present invention include the above named cationic initiators which can be employed alone or in admixture with a free radical initiator to provide a hybrid system.
  • Suitable free radical initiators include 1-hydrocyclohexyl phenyl ketone, 2-hydroxy-2-methyl-l-phen ⁇ l-l-propan-l-one, 2,2-dichloro- ⁇ -(4-phenoxy- phenyl) ethanone and the like.
  • the free radical component can comprise up to 75%, preferably between about 30 and about 70%, of the cationic initiator component.
  • a particularly pre erred initiator mixture includes between about 30 wt. % and about "40 wt.
  • the present initiator mixtures are recommended for blends of (b) and (c) where component (b) contains an acrylate.
  • the total amount of initiator employed is generally between about 0.l and about 5 wt. % with respect to reactant or reactants.
  • one or more of the present aliphatic alkenyl ethers can be employed or blended with one or more of the polymerizable epoxides, vinyl ethers, acrylates dr vinyloxy alkyl urethanes, thus benefiting from the properties cff 'each monomer in the blend.
  • blends of the present propenyl ether and the divinyl ether of dimethylol cyclohexane enhance solub ' flizafcifn of the cationic initiator.
  • Such blends may contain up to about 60%, preferably from about 20 to about 50% of component (b) .
  • the propenyl ether of component (c) in the present composition serves not only as a reactant, but also as an essential diluent for the vinyl ether and/or epoxide which compounds are highly viscous and difficult to apply as coatings.
  • the propenyl ether provides a coatable composition without the need for extraneous diluents which in many cases can cause blisters and non-uniformity in the coating product.
  • the compositions of the present invention are cured within a period of up to one second by exposure to a source of radiation, e.g. UV light, electron beam, laser emissions, gamma rays etc. Radiation curing in the present cationic system takes place at a fast rate, e.g.
  • UV light radiation dosages at room temperature of from about 100 to about 1500 milli J/cm 2 are effective and dosages of from about 200 to about 600 milli J/cm 2 are preferred.
  • Equivalent dosages for curing are employed when using alternative sources of radiation.
  • curing with electron beam radiation can be carried out at between about 0.5 and about 20 Mrads, preferably between about 1 and about 10 Mrads. Specific techniques for radiation curing are well known, thus further amplification is not required.
  • the present propenyl ethers are normally liquid, they can be directly mixed with the polymerizable vinyl ether, epoxide or vinyloxy alkyl urethane monomer or oligomer without further conditioning; however, in certain cases where dilution is desired, as in cases where higher molecular weight alkenyl ethers of this invention are employed as component (c) or where the blend provides a highly viscous mixtue, the alkenyl ether can be dissolved in an inert organic solvent such as methyl ethyl ketone, toluene, a hydrocarbon, acetone, an ether or a halogenated compound such as methylene chloride. However, dilution with the above solvents should not exceed 50% when highly resistant coatings are required.
  • the alkenyl ether monomer or oligomer in the absence of a comonomer can be applied directly to any of the above substrates and subjected to radiation for curing under the above conditions to form a more highly cross-linked homopolymeric protective coating.
  • the present compositions can optionally contain minor amounts of conventional adjuvants such as a surfactant e.g. a fluorocarbon surfactant such as a mixture of fluoroaliphatic polymeric esters or a silicane copolymer surfactant or others.
  • a surfactant e.g. a fluorocarbon surfactant such as a mixture of fluoroaliphatic polymeric esters or a silicane copolymer surfactant or others.
  • the present compositions can be cured thermally or by radiation induced free radical polymerization; however, an advantage of this invention is the ability to cure the compositions by cationically induced radiation which avoids the disadvantages discussed in the foregoing disclosure.
  • component (b) of the composition is an acrylate, e.g. bisphenol A epoxyacrylate.
  • the flask was heated to 55-60°C. for 4 hours, during which time 40 g. of ethanol by-product was taken off.
  • the vacuum was then removed and nitrogen gas was introduced.
  • the flask was then heated to 110°C. under ambient pressure. After 12 hours an additional 78 g. of ethanol by-product was removed.
  • the crude reaction product (463 g.) was flash distilled.
  • the main fraction (292 g.) distilling at 100-200°C. under 3 mm Hg was found to contain 85% tris (vinyl oxybutyl) ethyl orthosilicate and 15% bis (vinyl oxybutyl) ethyl orthosilicate.
  • B. A separate 50 g. portion of the crude reaction product was flash distilled at 210°C. , 1 mm Hg. Analysis of 47 g.
  • a 3-necked 100 ml round bottomed flask, equipped with a magnetic stirrer, vertical water condenser connected to vacuum via a trap and nitrogen gas inlet was charged with 25 g. of the above main fraction (Example IA) , 40 g. of hydroxybutyl vinyl ether and 0.5 g. of KOH.
  • the flask was heated to 100°C. under a blanket of nitrogen for a period of 5 hours after which the mixture was flash distilled, unreacted material removed at 100°C. under 3 mm Hg and the remaining distillate collected.
  • the collected distillate was found to be a mixture of 87% tris (vinyl oxybutyl ethyl) orthosilicate and 10% tetra (vinyl oxybutyl ethyl) orthosilicate.
  • Example 1 The main fraction of Example 1 (Part A) was mixed with an equal weight amount of the diglycidyl ether of bisphenol A (EPON-828, Shell), 1 part per hundred parts of resin of a fluorochemical surfactant (FC-430) , and 4 parts per hundred parts of resin of a cationic photoinitiator FX-512 at 50°C. until a homogeneous low viscosity liquid was obtained.
  • This mixture was then coated on an aluminum substrate at a thickness of 1.2 mil. The coated surface was exposed for less than 1 second to 400 millijoules/cm 2 from a mercury vapor lamp. A tack free, film was produced. Coating properties reported in the following table were determined immediately after UV exposure and after a post cure at 177°C. for 15 minutes. - 11 -
  • Example 3 The mixture described in Example 3 was coated on a polyester substrate at a thickness of 0.5 mil. The coated surface was exposed to 400 millijoules/cm 2 UV light for less than 1 second and post cured for 2 hours at 50°C. Chemical resistance was tested by the covered spot test (ASTM D 1308) . No attack was observed after 24 hours exposure to 1% H 2 S0 4 , 1% NaOH, 10% acetic acid, or distilled water.
  • Example 3 The mixture described in Example 3 was coated on an aluminum panel at a thickness of 0.25 mil. The coated surface was exposed to an electron beam dosage of 3 Mrads for less than 1 second to produce a tack free film. Coating properties reported in the following Table were determined immediately after electron beam exposure and after a post cure at 150°C. for 15 minutes. TABLE
  • Example 1 part A The main fraction of Example 1 part A (25.0 gm) was mixed with the divinyl ether of triethylene glycol (25.0 gm) a bisphenol A epoxy acrylate oligomer (EBECRYL-3700, Radcure Specialties, 50.0 gm) , 2 phr* cationic photoinitiator (FX 512) , 2 phr* free radical photoinitiator (IRGACURE-184) and 1 phr* fluorochemical surfactant (FC-430) at 50°C. until a homogeneous low viscosity liquid was obtained, this mixture was then coated on a polyester substrate at a thickness of 0.5 mil. The coated surface was exposed to 400 millijoules/cm 2 from a mercury vapor lamp for less than 1 second. A tack free coating with the following properties was produced.
  • Example l part A The main fraction from Example l part A (6.20 gm) was mixed with the divinyl ether of triethylene glycol (18.8 gm) and a divinyl ether urethane oligomer (prepared as described in the Degree Thesis of Lennart Carlsson, Dept. of Polymer Technology, The Royal Institute of Technology, Sweden, 1987; 25.0 gm) ; 4 phr cationic photoinitiator (FX-512) , and 1 phr fluorochemical surfactant (FC.-430) at 50°C. until a homogeneous low viscosity liquid was obtained.
  • This mixture was then coated on a aluminum panel (0.25 mil) and exposed to 400 millijoules/cm 2 from a mercury vapor lamp for less than 1 second. A tack free coating with the following properties was produced
  • the coated substrate was then exposed for less than one second at room temperature to 400 milli J/cirr radiation from a medium pressure mercury vapor lamp; after which the substrate having a highly crosslinked strongly adhesive coating* was removed.
  • the coating is resistant to attack by methyl ethyl ketone and is abrasion resistant.
  • a two mil thick layer of a mixture of 98 wt. % of the tetraprop-1-enyl ether of pentaerythritol and 2.0 wt. % of the triphenyl sulfonium salt of hexafluorophosphate is applied to a polyester substrate.
  • the coated layer is then crosslinked by exposure for about one second at room temperature to electron beam radiation at a dosage of 3 Mrad.
  • the resulting highly crosslinked polymer exhibits strong adhesion, is highly resistant to chemical attack and has superior abrasion resistant properties.
  • Example 8 Each of the samples A, B, and C were coated in a thickness of 0.11-0.15 mil on an aluminum panel and then cured by exposure to UV light as described in Example 8. The cured coatings were evaluated and the results are reported in the following Table.
  • Example 10 also demonstrates the high cure speed of the di-propenyl ethers as compared to the di-epoxy compound.
  • This example illustrates the necessity of the cationic photoinitiator and the superior solvent resistance obtained using a cationic and free radical initiator.
  • Example 11A is repeated except that the 50 grams of cis,cis- dipropenyl ether of triethylene glycol is replaced with 50 grams of a 1 to l wt. % blend of cis,cis- dipropenyl ether of triethylene glycol and the divinyl ether of 1,4-cyclohexane dimethanol.
  • Example 11A is repeated except that the 50 grams of cis,cis- dipropenyl ether of triethylene glycol is replaced with 50 grams of the divinyl ether of 1,4-cyclohexane dimethanol.
  • the cationic initiator failed to dissolve in the absence ' of the propenyl ether and an in compatible mixture was formed.
  • This example illustrates that coating hardness can be significantly improved by adding the divinyl ether of 1,4-cyclohexane dimethanol; and that, the dipropenyl ether of triethylene glycol is needed to insure compatibility.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Epoxy Resins (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Silicates d'éther alk-1-ényle de la formule (I): [X]4-nSi[OR1OCH=CH-R2]n, et procédé de production desdits silicates, X étant un halogène ou -OR, R étant un alkyle inférieur ou un mélange d'halogène et d'OR, un mélange d'OR et d'hydrogéne ou un mélange d'halogène et d'hydrogène; R1 contenant 1 à 8 atomes de carbone et étant un alkylène, un alkénylène, un alkynylène, optionnellement alkoxylés avec jusqu'à 20 unités de α, Y étant de l'hydrogène ou du méthyle et R2 étant chacun de l'hydrogène ou un alkle inférieur et n ayant une valeur de 1 à 4; et éther alkényle polyfonctionnel de la formule (II): A[(CH2O)m(Z)zCH=CHR]n, A étant un atome de carbone, un -OCH=CHR ou un [aklyle C1 à C10]4-n; R étant un alkyle C1 à C6; Z étant un alkylènéoxy C2 à C8; r ayant une valeur de 0 à 6; m ayant une valeur de 0 à 1 et l'un des deux au moins, de r et m, ayant une valeur positive; n ayant une valeur de 1 à 4, à condition que m soit égal à 0 et que n soit égal à 1 lorsque A est un -OCH=CHR, que n ait une valeur de 2 ou 3 lorsque A est un [alkyle C1 à C10]4-n et que n ait une valeur de 4 lorsque A est du carbone. La présente invention décrit également des compositions réticulables, polymérisables par radiation contenant (a) de 0,1 à environ 5 % en poids d'un initiateur contenant au moins 25 % d'initiateur cationique, (b) d'environ 0 à environ 60 % en poids d'un éther vinylique, d'un époxyde, d'un uréthane ou d'un acrylate vinyloxy alkyl polymérisables et (c) d'environ 35 à environ 99,9 % en poids d'un éther de la formule (II).
PCT/US1990/006758 1990-01-26 1990-11-23 Ethers alkenyles et compositions polymerisables par radiation WO1991011467A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US470,489 1990-01-26
US07/470,487 US5045572A (en) 1990-01-26 1990-01-26 Radiation curable cross linkable compositions containing an aliphatic polyfunctional alkenyl ether
US07/470,489 US5039716A (en) 1990-01-26 1990-01-26 Alk-1-enyl ether silicates and radiation curable composition containing alk-1-enyl ether silicates
US470,487 1990-01-26

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WO1992022609A1 (fr) * 1991-06-13 1992-12-23 Teroson Gmbh Produit d'etancheite et adhesifs a base de prepolymeres modifies par des silanes
US5384342A (en) * 1993-08-30 1995-01-24 Dsm Desotech, Inc. Vinyl ether urethane silanes
DE19500241A1 (de) * 1995-01-05 1996-07-11 Thera Ges Fuer Patente Radikalisch polymerisierbare Zubereitungen und ihre Verwendung
EP0826718A2 (fr) * 1996-09-03 1998-03-04 Dow Corning Corporation Fibres SiCO amorphes et fibres SiC cristallins à partir de résines de polysiloxanes durcissables ayant des groupes alk-1-ényléther
EP0979233A1 (fr) * 1997-04-21 2000-02-16 NeXstar Pharmaceuticals, Inc. Synthese d'oligonucleotides en solution
EP1004602A1 (fr) * 1998-11-25 2000-05-31 Dow Corning Corporation Polyisobutylènes fonctionnalisés d'éthers alcényliques et leur procédé de préparation
US6187834B1 (en) * 1999-09-08 2001-02-13 Dow Corning Corporation Radiation curable silicone compositions
JP2019011296A (ja) * 2017-06-30 2019-01-24 協立化学産業株式会社 新規重合性化合物及び柔軟性樹脂組成物
CN113755046A (zh) * 2020-06-03 2021-12-07 三星Sdi株式会社 用于封装有机发光二极管的组合物和包括由其形成的有机层的有机发光二极管显示器
CN117601456A (zh) * 2024-01-22 2024-02-27 四川省宜宾普什建材有限责任公司 一种大口径的电热熔式塑料管件的加工工艺

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US3842019A (en) * 1969-04-04 1974-10-15 Minnesota Mining & Mfg Use of sulfonic acid salts in cationic polymerization
US3804795A (en) * 1972-11-06 1974-04-16 Dow Chemical Co High molecular weight resins having low solution viscosities
US4654379A (en) * 1985-12-05 1987-03-31 Allied Corporation Semi-interpenetrating polymer networks
JPS6429450A (en) * 1987-07-24 1989-01-31 Dainippon Ink & Chemicals Curable resin composition
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Cited By (14)

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CN117601456B (zh) * 2024-01-22 2024-03-26 四川省宜宾普什建材有限责任公司 一种大口径的电热熔式塑料管件的加工工艺

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CA2031114A1 (fr) 1991-07-27

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