CN85101534A - The method of curable synthetic resin composition and manufacturing multipolymer - Google Patents
The method of curable synthetic resin composition and manufacturing multipolymer Download PDFInfo
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- CN85101534A CN85101534A CN85101534.4A CN85101534A CN85101534A CN 85101534 A CN85101534 A CN 85101534A CN 85101534 A CN85101534 A CN 85101534A CN 85101534 A CN85101534 A CN 85101534A
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 229920003002 synthetic resin Polymers 0.000 title claims description 52
- 239000000057 synthetic resin Substances 0.000 title claims description 52
- 239000000203 mixture Substances 0.000 title claims description 41
- -1 polysiloxane Polymers 0.000 claims abstract description 39
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 9
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical group C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 239000000543 intermediate Substances 0.000 claims description 6
- 125000000962 organic group Chemical group 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 claims description 3
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 2
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims description 2
- 239000012264 purified product Substances 0.000 claims description 2
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 claims description 2
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 claims 1
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical compound OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 claims 1
- 125000003963 dichloro group Chemical group Cl* 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 230000007704 transition Effects 0.000 abstract description 6
- 238000007711 solidification Methods 0.000 abstract description 5
- 230000008023 solidification Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 229920001296 polysiloxane Polymers 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000008859 change Effects 0.000 abstract description 2
- 239000003365 glass fiber Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 abstract 1
- 125000003944 tolyl group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 239000002253 acid Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 2
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- XOMKZKJEJBZBJJ-UHFFFAOYSA-N 1,2-dichloro-3-phenylbenzene Chemical group ClC1=CC=CC(C=2C=CC=CC=2)=C1Cl XOMKZKJEJBZBJJ-UHFFFAOYSA-N 0.000 description 1
- QCQRDQXUCCYINJ-UHFFFAOYSA-N 1-(2-hexoxyphenyl)ethanone Chemical compound CCCCCCOC1=CC=CC=C1C(C)=O QCQRDQXUCCYINJ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 description 1
- JECYUBVRTQDVAT-UHFFFAOYSA-N 2-acetylphenol Chemical compound CC(=O)C1=CC=CC=C1O JECYUBVRTQDVAT-UHFFFAOYSA-N 0.000 description 1
- OCIFJWVZZUDMRL-UHFFFAOYSA-N 6-hydroxyhexyl prop-2-enoate Chemical compound OCCCCCCOC(=O)C=C OCIFJWVZZUDMRL-UHFFFAOYSA-N 0.000 description 1
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- QLNWYPZFNHLJGO-UHFFFAOYSA-N dichloromethyl(phenyl)silane Chemical class ClC(Cl)[SiH2]C1=CC=CC=C1 QLNWYPZFNHLJGO-UHFFFAOYSA-N 0.000 description 1
- XUKFPAQLGOOCNJ-UHFFFAOYSA-N dimethyl(trimethylsilyloxy)silicon Chemical compound C[Si](C)O[Si](C)(C)C XUKFPAQLGOOCNJ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001327 prunus amygdalus amara l. extract Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
But the invention provides the new solidity polysiloxane coating materials and the manufacture method thereof of a kind of clad opticglass and so on usefulness.
The existence that various acrylate are rolled into a ball can increase solidification rate.With the contained various dimethyl siloxane of change group, the method for ratio between methylphenyl siloxane group and the diphenyl siloxane group can be regulated refractive index (surpassing 1.46) and second-order transition temperature (being lower than-50 ℃).With the method for adding the monomer acrylic compound, can further improve solidification rate.
Except high solidification rate, this coating material also have wettability good (can be on glass fibre coating at a high speed and under the high temperature yet formation of droplets), advantage such as mechanical property is suitable and stability in storage is good.
Description
The present invention relates to contain a kind of curable synthetic resin composition of multipolymer.This multipolymer has the monomeric unit of being made up of dimethyl siloxane and at least one siloxanes of selecting from methylphenyl siloxane and diphenyl siloxane.
The invention still further relates to a kind of manufacture method of multipolymer.This multipolymer has the monomeric unit of being made up of dimethyl siloxane and at least one siloxanes of selecting from methylphenyl siloxane and diphenyl siloxane.
For instance, curable synthetic resin composition made in accordance with the present invention can be used as the coating of optical glass fibre.
This synthetic resin coating is different from US Patent specification 4,270, is proposed in 840.Reaction causes temperature rise by all vinyl groups under the influence of platinic compound catalyzer (0.2～3 heavy %), and this synthetic resin coating is solidified.When having bitter almond oil camphor to make initiator, also can realize solidifying, so that obtain higher curing speed with light-struck method.In the back in this case, must do assisted reaction group with vinyl group and sulfydryl group or acryloyl group.Because the curable synthetic resin composition of the above-mentioned type does not contain solvent, thereby do not have compound when solidifying and run out of.So this curing can be accomplished the harm of not only fast but also nonpollution environment.
For the synthetic resin coating of making according to above-mentioned United States Patent (USP), the kinematic viscosity before it solidifies is 5 * 10
-4With 1 meter
2Between/second, the Young's modulus after the curing is lower than 2 crust, and the refraction index N D in the time of 25 ℃ is between 1.40 and 1.52.Can be by the ratio between dimethyl siloxane and the methylphenyl siloxane in the change multipolymer, the birefringence index is regulated.Coating speed during the coating glass fibre is 0.5 to 2 meter per second.
Purpose of the present invention is in order to provide be shorter than 5 seconds a kind of set time, preferably to be shorter than 0.5 second curable synthetic resin composition.For instance, because the result who shortens set time, the fiber speed of coated optics glass can surpass 5 meter per seconds.
The invention still further relates to the curable synthetic resin composition that on fast mobile substrate, stays even no dropping point coating.
Another object of the present invention, provide a kind of form after the curing Young's modulus between 0.1 and 10 crust with refractive index greater than 1.46(preferably 1.48) curable synthetic resin composition.
Another purpose more of the present invention provides have the curable synthetic resin composition this additional requirement and low Tg (best-case is to be lower than-50 ℃) that do not flow when about 250 ℃ of temperature.
Last purpose of the present invention provides the method for curable synthetic resin composition with multipolymer of making.
According to the present invention, adopt the curable synthetic resin composition that contains molecular formula multipolymer as follows, can satisfy above-mentioned requirements.
In the formula: R
1And R
8Be from groups, aryl group and contain the organic group that selects the groups of acrylate; R
2, R
3, R
4, R
6And R
7It is the organic group that from groups and aryl group, selects; R
5It is the organic group that contains acrylate.The molecular-weight average of polymkeric substance is between 1000 to 1000000.The scope of the shared average score of various monomeric units is as follows in each polymer molecule:
0.005≤p≤0.995
0 ≤q≤0.995
0 ≤r≤0.49
0 ≤S≤0.1
Wherein: 0.005≤(q+2r)≤0.995, monomeric unit wherein can be agglomerating, alternately or randomly be distributed in the molecule, and wherein each copolymer molecule contains 2 acrylate groups at least.
Selected groups, preferably the short-chain alkyl group of Me and ethyl group and so on.Suitable aryl group is phenyl group and phenmethyl group.
The groups that contains acrylate is the following group of molecular formula:
R in the formula
9Be the groups of divalence, for example ,-(CH
2) n-, n 〉=1.
When the agglomerating distribution of the monomeric unit in the copolymer molecule, in some groups that are combined into by the different monomers unit, there is identical monomeric unit.When the monomeric unit in the copolymer molecule was alternately distributed, one type monomeric unit was always replaced by the monomeric unit of another kind of type on the polymer chain, and formed quite neat structure.When the monomeric unit random distribution in the copolymer molecule, various types of monomeric units at random are distributed on the polymer chain, form length and form the various groups that all differ.
According to the present invention, the R in the suitable curable synthetic resin composition
5, be the groups that contains acrylate.
If the S value is not to select too for a short time, curing speed is high so.Be positioned at the R of reaction group at polymkeric substance center
5Mobility less, so its speed of reaction is than the R of reaction group that is positioned at end group
1And R
2Low, but because its quantity is quite a lot of, so still can shorten set time significantly.According to the present invention, S has good result of use greater than 0.02 curable synthetic resin composition.
According to the present invention, the r and the S of the curable synthetic resin composition that another is suitable are equal to 0, and R
1And R
8It is the groups that contains acrylate.
If owing on the polymer molecule side chain is arranged, make reactive end group in the molecule more than 2, that also can obtain high solidification rate.According to the present invention, if R
5Be and the polymer molecule main chain average polysiloxane chain of forming that contains acrylate of the same type and same, the curable synthetic resin composition that can obtain suiting so.
With uv irradiation method or electron radiation method, can solidify the synthetic resin coating of making by the present invention.If carry out curing with uv irradiation method, must in synthetic resin coating, add photoinitiator so.In order in curable synthetic resin composition, to dissolve in the photoinitiator of capacity, must make (+2r) greater than 0.3.The presentation of results of doing like this in order to guarantee the solubleness of initiator, must have enough aryl groups (phenyl group) to exist.
If make synthetic resin coating contain the photoinitiator of 1 to 5 heavy %, the UV-light-curable synthetic resin composition that can obtain suiting so.
Being used for UV-light-curable synthetic resin composition best photoinitiator that produces effects, is to be selected from 2,2-dimethoxy-2-phenyl-phenyl methyl ketone, 2,2-two hexyloxy-phenyl methyl ketone and 2,2-dimethyl-these compounds of 2-hydroxyl-phenyl methyl ketone.
If synthetic resin coating contains some monomer acrylic compound, can obtain extra high curing speed so.In order not influence other character, effective means is to allow synthetic resin coating contain 0 to 20 heavy compound %, that have some monomer acrylate.
From hexanediyl ester, 2-oxyethyl group-ethyl propylene acid esters, 2 '-select oxyethyl group-2-oxyethyl group-ethyl propylene acid esters and these chemicals of Viscoat 295 the monomer acrylic compound have good result of use.
According to another aspect of the present invention, the method that the present invention makes new synthetic resin coating comprises following steps:
A) make by dichlorodimethylsilane, carboxylic acid and solution that some are made up of the compound of selecting in dichloromethyl phenylsilane, dichloro diphenyl silane, two chloro-methyl hydrogen silane, a Chlorodimethyl hydrogen silane, trichloromethyl silane and these compounds of trichlorophenyl silane.According to the composition of the desired multipolymer that obtains, select the allotment ratio of above-claimed cpd.
B) alkanol of a great deal of is added solution, so that hydrolysis and polymerization take place.
C) heated solution is till in fact hydrolysis is finished.
D) use known method, make polymer intermediates and byproduct and separated from solvent.
E) dissolving high molecular intermediates, and add catalyzer.
F) the unsaturated chain alkanol of adding a great deal of.
G) heated solution is till in fact reaction is finished.
H) remove catalyzer.
I) vinylformic acid muriate (acrylic acid chloride) is added solution.
J) heated solution is till in fact reaction is finished.Use known method, remove the hydrogenchloride that is generated.
K) product is separated with byproduct, and use the currently known methods purified product.
Use below with reference to concrete manifestation and diagrammatic method, the present invention is done comparatively detailed explanation.
Fig. 1 represents the concrete manifestation according to method of the present invention.
Fig. 2 a represents 2, the molecular formula of 2-methoxyl group-2-phenyl-phenyl methyl ketone.
Fig. 2 b represents 2, the molecular formula of 2-diethoxy-phenyl methyl ketone.
Fig. 2 c represents 2, the molecular formula of 2-dimethyl-2-hydroxyl-ethylbenzene acyl.
Fig. 3 a represents the acrylic acid molecular formula of ethylene glycol bisthioglycolate.
Fig. 3 b represents the molecular formula of 2-oxyethyl group-ethyl propylene acid esters.
Fig. 3 c represents 2 '-molecular formula of oxyethyl group-2-oxyethyl group-ethyl propylene acid esters.
Fig. 3 d represents the molecular formula of trimethylolpropane tris propylene ester.
Concrete manifestation according to method of the present invention.
With dichlorodimethylsilane (a), dichloromethyl phenyl silane (b) and a Chlorodimethyl hydrogen alkane (c),, be dissolved in the acetate in meeting the ratio that the desired multipolymer that obtains is formed.Also can use other solution.In order to obtain desired response, must use carboxylic acid.Adopting the benefit of acetic acid solvent and reagent is to make polyreaction produce the high molecular and the acyclic polysiloxane molecule of big share.For example, for the polysiloxane of P-q=0.5 and molecular-weight average 10000 is provided, must adopt by 32 gram dichlorodimethylsilane, 48 gram dichloromethyl phenyl silanes, 1 gram one Chlorodimethyl hydrogen silane and 500 milliliters of solution that acetate is made into.Under the situation that this solution refluxes, stir on one side, one side drop by drop adds solution with the methyl alcohol of a great deal of.Compare with other alkanols, adopt methyl alcohol to have the advantage of telling the reaction byproduct that produces at low temperatures.
Keep this solution under boiling state 2 hours, to be hydrolyzed and polymerization.Under 58 ℃ of temperature, fractionate out the methyl ethyl ester that is produced, at 150 ℃ of temperature and pressure 2 * 10
4Fractionate out low molecule and the lower siloxanes of number of rings under the handkerchief.P/q ratio in the a/b ratio decision solution.C/(a+b) molecular weight of ratio decision the finished product.
Except that above-mentioned siloxanes, also available dichloro diphenyl siloxane.Because its diphenyl siloxane group is bonded in the polymkeric substance, institute is so that r is not equal to zero.Contain acrylate groups R for what will participate in reaction
5Be attached in the molecule, must add two chloro-methyl hydrogen silane.In order to provide the polymer chain of side chain, can add dichlorodimethylsilane or trichlorophenyl silane.But consumption can not be too big, because can produce other gels.
The high-molecular weight intermediate product is dissolved in the Anaesthetie Ether that contains catalytic amount, also can use other solvents, for example, tetrahydrofuran (THF).Effectively catalytic amount is every liter several milligrams.For example, 50 gram intermediates are dissolved in 200 milliliters of Anaesthetie Ethers that contain 1 milligram of chloroplatinic acid.Can be with other platinic compound, for example the organic acid of platinic acid or palladium compound replace chloroplatinic acid.Under the situation that this solution refluxes, stir on one side, the alkanol with a great deal of drop by drop adds solution on one side.Keep this solution under boiling state 4 hours, then the elimination catalyzer.
Under this solution ebullient situation, stir on one side, one side drop by drop adds solution with the Trimethylamine and the vinylformic acid muriate of a great deal of.Keep this solution under the ebullient state 2 hours, the triethyl ammonium chloride that elimination then generated.In order to retrain formed HCl, can use various nitrogenous organic basess, the bubble that it can alveolation imaging air sample, by solution, the band step HCl that generates.
Can purify product, for example use the alkali liquid washing secondary of 0.2N NaOH, use anhydrous MgSO then
4Dry.The multipolymer of gained can be delivered for use after boiling off solvent.Requiring under the situation of standing storage, effectively way is to add stablizer in multipolymer.Quinhydrones-methyl ether of 500PPm for example.
Have many conspicuous changeable parts in the aforesaid method, for example can replace fractionating process to separate intermediates and the finished product with extraction process, these certainly all within the scope of the present invention.
The example of curable synthetic resin composition of the present invention.
Multipolymer according to aforesaid method is made does not need to add any material again, just can be used as curable synthetic resin composition.Under this occasion, be that 100 to 500 kiloelectron-volts electron irradiation is cured with energy.For example, there is a kind of electrical screen equipment (product of Massachusetts Woburn energy scientific company) to be applicable to this purpose.
If 2 of 4 heavy %, (Fig. 2 a) photoinitiator adds in the curable synthetic resin coating 2-dimethoxy-2-phenyl methyl phenyl ketone, and it is possible solidifying with uv irradiation method.For example, can produce wavelength is that 200 to 400 millimicrons, the intensity on synthetic resin coating are 0.5 watt/centimetre
2The high pressure mercury vapour lamp of illumination be to be applicable to solidified.Solidifying the required time depends on the composition of curable synthetic resin composition, generally below 5 seconds.
Table 1 has been enumerated some character that contains the curable synthetic resin composition of various ratio monomeric unit multipolymers of the present invention.Tg is the second-order transition temperature after the material cured, and coating presents the temperature like rubber properties when promptly surpassing this temperature.n
25 DIt is coating refractive index in the time of 25 ℃ before solidifying.
Table 1
P Q S T
g（℃） n
25 D
0.60 0.40 0 -80 1.481
0.39 0.61 0 -55 1.506
0.41 0.58 0.01 -59 1.503
0.49 0.49 0.02 -60 1.500
0.69 0.25 0.06 -94 1.461
0.56 0.38 0.06 -77 1.478
It seems that from table 1 when the amount of dimethyl siloxane increased, vitrified temperature reduced.On the other hand, when the amount of methylphenyl siloxane or diphenyl siloxane increased, refractive index increased.
M
n=14,000, the refractive index n of P=q=0.49 and S=0.02 curable synthetic resin composition
25 DBe 1.4998, viscosity was 530 milli handkerchief seconds in the time of 25 ℃, and viscosity was 210 milli handkerchief seconds in the time of 45 ℃.Reach 1500 seconds in shearing rate
-1The time, curable synthetic resin composition presents Newtonian behaviour.Described coating refractive index n of (as above-mentioned, with uviolizing 5 seconds) after curing
25 DBe 1.5030, second-order transition temperature T
gBe-60 ℃, Young's modulus is 0.15 MPa.
Molecular weight M
nIt is the number-average molecular weight of multipolymer.
If the monomer acrylic compound of some auxilliary reactions is added in the curable synthetic resin coating, curing speed can be accelerated.Add hexanediyl ester (HDDA as can be seen from Table 2, Fig. 3 a), 2 '-oxyethyl group-2-oxyethyl group-ethyl propylene acid esters (EEEA, Fig. 3 c) or the influence of Viscoat 295 (TMPTA, Fig. 3 d), also show some character of solidify material in the table.Used multipolymer is same as described above.Be the required time of non-sticky surface of obtaining when being cured with the ultraviolet ray of above-mentioned lamp method set time.
Table 2
HDDA EEEA TMPTA T set time
gn
25 D
(heavy %) (heavy %) (heavy %) (second) (℃)
0 0 0 4.8 -60 1.503
10 0 0 0.12 -57 1.504
20 0 0 0.06 -57 1.505
0 10 0 2.4 -60 1.500
0 20 0 2.3 -60 1.496
0 0 20 0.05 -57 1.507
When obvious raising hexylene glycol acrylate
*Or during the add-on of Viscoat 295, the speed of response surge.The addition of monomer acrylate increases to 20 heavy % by 0, and the second-order transition temperature increase is very little, and therefore the seemingly rubber properties to cured product can not produce injurious effects.Influence to refractive index is small, and the variation of refractive index is generally in the close limit of desired value.
Can it be the filler of routine 40.0 meters as surface-area in addition
2The SiO of/gram
2,
, add in the curable synthetic resin composition.Also can add flow promoting agent, for example, hexamethyldisiloxane, acryloxy (acryloxy) propyl group pentamethyl disiloxane and two propylene acyloxy propyl group tetramethyl disiloxanes.
Though curable synthetic resin composition of the present invention has high solidification rate, it is still stable before using, therefore can standing storage.If curable synthetic resin composition is used for the high-temperature material surface, its wettability also is good (not formation of droplets).In addition, above-mentioned synthetic resin coating also has more than second-order transition temperature non-crystallizable, though under near the low temperature of second-order transition temperature also non crystallized advantage, so the Young's modulus value is also low.
*Sic may be mistake-translator of hexanediyl ester.
Errata CPCH 856024
Claims (11)
1, the curable synthetic resin composition that contains a kind of multipolymer.This multipolymer has the monomeric unit of being made up of dimethyl siloxane and at least one siloxanes of selecting from methylphenyl siloxane and diphenyl siloxane.The characteristics of this coating that requires according to the present invention are that polymkeric substance wherein is the following a kind of compound of molecular formula:
In the formula: R
1And R
8Be from groups, aryl group and contain the organic group that selects the groups of acrylate, R
2, R
3, R
4, R
6And R
7Be the organic group that from groups and aryl group, selects, R
5It is the organic group that contains acrylate.The molecular-weight average of polymkeric substance is 1,000 to 1,000, and between 000, the scope of the shared average score of various monomeric units is as follows in every polymer molecule:
0.005≤p≤0.995
0≤q≤0.995
0≤r≤0.49
0≤s≤0.1
Wherein 0.005≤(q+2r)≤0.995 and monomeric unit wherein can be agglomerating alternately or randomly be distributed in the molecule and every copolymer molecule wherein contains two acrylate groups at least.
2, the characteristics according to the curable synthetic resin composition of claim 1 are R wherein
5Be one and contain acrylate group alkyl.
3, the characteristics according to the curable synthetic resin composition of claim 1 or 2 are that S wherein is greater than 0.02.
4, the characteristics according to the curable synthetic resin composition of claim 1 are that wherein r and S equal zero R
1And R
8For containing the groups of acrylate.
5, the characteristics according to the curable synthetic resin composition of claim 1 are R wherein
5Be and the isostructural and same average polysiloxane chain of forming that contains acrylate of polymer molecule main chain.
6, the characteristics according to the curable synthetic resin composition of claim 1 to 5 are that wherein (q+2r) is greater than 0.3.
7, the characteristics according to the curable synthetic resin composition of claim 6 are, contain the photoinitiator of 1 to 5 heavy % in the synthetic resins composition wherein.
8, the characteristics according to the curable synthetic resin composition of claim 7 are that photoinitiator wherein is to be selected from 2,2-dimethoxy-2-phenyl-methyl phenyl ketone, 2,2-diethoxy acetophenone and 2,2-dimethyl-these compounds of 2-hydroxy acetophenone.
9, the characteristics according to the curable synthetic resin composition of claim 1 to 8 are, wherein synthetic resin coating contains some monomer acrylic compound of 0 to 20 heavy %.
10, the characteristics according to the curable synthetic resin composition of claim 9 are, monomer acrylic compound wherein be select oneself omega-diol diacrylate, 2-ethoxyethyl group acrylate, 2 '-oxyethyl group-2-ethoxyethyl group acrylate and these compounds of Viscoat 295.
11, the manufacture method that contains the multipolymer of the monomeric unit of forming by dimethyl siloxane and siloxanes that at least one is selected from methylphenyl siloxane and diphenyl siloxane.The characteristics of this manufacturing process are to comprise the following step:
A) solution is made up of dichlorodimethylsilane, carboxylic acid and compound that some are selected from dichloromethyl phenyl silane, dichloro diphenyl silane, dichloro monomethyl hydrogen silane, a Chlorodimethyl hydrogen silane, trichloromethyl silane and these compounds of trichlorophenyl silane of preparation is according to the ratio of the composition selection above-claimed cpd of requirement multipolymer.
B) alkanol of a great deal of is added in the solution, so that hydrolysis and polymerization take place.
C) heated solution is till in fact hydrolysis is finished.
D) make high-molecular weight intermediates and byproduct and separated from solvent with currently known methods.
E) dissolving high-molecular weight intermediates, and add catalyzer.
F) the unsaturated chain alkanol of adding a great deal of.
G) heated solution, till in fact reaction is finished,
H) remove catalyzer.
I) vinylformic acid muriate (acrylic acid chloride) is added in the solution.
J) heated solution till in fact reaction is finished, is got rid of the HCl that is generated with known method.
K) product is separated with byproduct, and with known method purified product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85101534 CN1010319B (en) | 1984-06-22 | 1985-04-01 | Curable synthetic resin coating and preparation method thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8401981A NL8401981A (en) | 1984-06-22 | 1984-06-22 | OPTICAL GLASS FIBER PROVIDED WITH A PLASTIC COATING AND METHOD FOR THE MANUFACTURE THEREOF. |
| CN 85101534 CN1010319B (en) | 1984-06-22 | 1985-04-01 | Curable synthetic resin coating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85101534A true CN85101534A (en) | 1987-01-17 |
| CN1010319B CN1010319B (en) | 1990-11-07 |
Family
ID=25741436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85101534 Expired CN1010319B (en) | 1984-06-22 | 1985-04-01 | Curable synthetic resin coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1010319B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061364C (en) * | 1997-10-15 | 2001-01-31 | 上海市建筑科学研究院 | Silicon propyl resin for paint and its producing method |
| CN1074034C (en) * | 1995-10-27 | 2001-10-31 | 株式会社小糸制作所 | Color coating composition for turn signal lamp and turn signal lamp |
| CN1102949C (en) * | 1997-05-01 | 2003-03-12 | 玻璃纤维四季服有限公司 | Coating composition with improved water and mar resistance |
| CN100383200C (en) * | 1998-02-17 | 2008-04-23 | 纳幕尔杜邦公司 | Method for forming powder coatings |
| CN100386385C (en) * | 2005-02-24 | 2008-05-07 | 瓦克化学股份公司 | Silicone rubber composition and silicone elastomer obtained therefrom with sustained load resistance |
| CN101497743B (en) * | 2008-01-04 | 2013-01-30 | 尼克桑斯公司 | Photocrosslinkable composition comprising polyorganosiloxane |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4555061B2 (en) * | 2004-09-28 | 2010-09-29 | Ｊｓｒ株式会社 | Radiation curable liquid resin composition for optical fiber up jacket |
-
1985
- 1985-04-01 CN CN 85101534 patent/CN1010319B/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074034C (en) * | 1995-10-27 | 2001-10-31 | 株式会社小糸制作所 | Color coating composition for turn signal lamp and turn signal lamp |
| CN1102949C (en) * | 1997-05-01 | 2003-03-12 | 玻璃纤维四季服有限公司 | Coating composition with improved water and mar resistance |
| CN1061364C (en) * | 1997-10-15 | 2001-01-31 | 上海市建筑科学研究院 | Silicon propyl resin for paint and its producing method |
| CN100383200C (en) * | 1998-02-17 | 2008-04-23 | 纳幕尔杜邦公司 | Method for forming powder coatings |
| CN100386385C (en) * | 2005-02-24 | 2008-05-07 | 瓦克化学股份公司 | Silicone rubber composition and silicone elastomer obtained therefrom with sustained load resistance |
| CN101497743B (en) * | 2008-01-04 | 2013-01-30 | 尼克桑斯公司 | Photocrosslinkable composition comprising polyorganosiloxane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1010319B (en) | 1990-11-07 |
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