CN1010319B - Curable synthetic resin coating and preparation method thereof - Google Patents
Curable synthetic resin coating and preparation method thereofInfo
- Publication number
- CN1010319B CN1010319B CN 85101534 CN85101534A CN1010319B CN 1010319 B CN1010319 B CN 1010319B CN 85101534 CN85101534 CN 85101534 CN 85101534 A CN85101534 A CN 85101534A CN 1010319 B CN1010319 B CN 1010319B
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- synthetic resin
- resin coating
- curable synthetic
- multipolymer
- acrylate
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Abstract
The invention provides a kind of new curable poly-oxosilane coating and manufacture method thereof that for example is used for the coated optics glass fibre.Various acrylate-based existence can increase solidification rate.With the method that changes the ratio between contained various dimethyl siloxane, methylphenyl siloxane base and the diphenyl siloxane base, can regulate 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 fibers line coating at a high speed and under the high temperature yet the Generation Liquid tool functional with advantages such as stability in storage is good.
Description
The present invention relates to a kind of curable synthetic resin coating that contains multipolymer.Multipolymer wherein has a kind of dimethyl siloxane and at least a monomeric unit that is selected from the siloxanes of methylphenyl siloxane and diphenyl siloxane of containing.
The invention still further relates to a kind of manufacture method of multipolymer.This multipolymer has by dimethyl siloxane and at least a monomeric unit that is selected from the siloxanes of methylphenyl siloxane and diphenyl siloxane.
For instance, curable made in accordance with the present invention synthetic resin coating can be used for the coated optics glass fibre.
This synthetic resin coating is in US Patent specification 4,270, proposes in 840.By making vinyl (0.2-3%(weight) improving temperature under the influence of platinic compound catalyzer) between react, 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.Under latter event, vinyl and sulfydryl or acryl are as common reactive group.Because the synthetic resin coating consolidated 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.
According to the synthetic resin coating that above-mentioned United States Patent (USP) is made, the dynamic viscosity before it solidifies is 5 * 10
-4With 1 meter
2Between/second, the Young's modulus after the curing is lower than 2 MPas (MPa), the refractive index n in the time of 25 ℃
DBetween 1.40 and 1.52.Can regulate refractive index by the ratio between dimethyl siloxane and the methylphenyl siloxane in the selection multipolymer.When the coating glass fibre, can obtain the coating speed of 0.5 to 2 meter per second.
The purpose of this invention is to provide and be shorter than 5 seconds a kind of set time, preferably be shorter than 0.5 second curable synthetic resin coating.For instance, because the result who shortens set time, coated optics glass fibre speed can surpass 5 meter per seconds.
The invention still further relates to a kind of curable synthetic resin coating that even dripless coating can be provided on the quick travel substrate.
Another object of the present invention provide a kind of form after the curing Young's modulus between 0.1 and 10 MPas (MPa) and refractive index greater than 1.46(preferably 1.48) curable synthetic resin coating.
A further object of the present invention provides a kind ofly has low Tg (preferably being lower than-50 ℃) and at do not flow during up to the 250 ℃ curable synthetic resin coating of this additional requirement of temperature.
Last purpose of the present invention provides the manufacture method of the multipolymer that is used for curable synthetic resin coating.
According to the curable synthetic resin coating that contains the multipolymer shown in the following formula of the present invention, can satisfy above-mentioned requirements.
In the formula: R
1And R
8Be to be selected from alkyl, aryl and to contain organic group in the alkyl of acrylate; R
2, R
3, R
4, R
6And R
7It is the organic group that is selected from alkyl and aryl; R
5It is the organic group that contains acrylate.The molecular-weight average of polymkeric substance is 1,000 to 1,000, between 000.The shared average score of various monomeric units is in following limited range 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 block, alternately or random mode be distributed in the molecule, wherein each copolymer molecule contain at least two acrylate-based.
Alkyl preferably is selected from the short-chain alkyl of methyl and ethyl and so on.Suitable aryl such as phenyl and phenmethyl.
The alkyl that contains acrylate be as shown in the formula group:
-R
9-O-
-CH＝CH
2
R in the formula
9Be the alkyl of divalence, for example ,-(CH
2) n-, n 〉=1.
When the monomeric unit in the copolymer molecule was pressed block distributed, identical monomeric unit was present in one or more bases, and these bases are connected with one or more bases of being made up of other monomeric units.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, formed quite regular structure.When the monomeric unit random distribution in the copolymer molecule, various types of monomeric units at random are distributed on the chain of polymkeric substance all lengths and on forming.
According to suitable curable synthetic resin coating of the present invention, wherein R
5It is the alkyl 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 reactive group R at polymer chain center
5Mobility less, so its speed of reaction is than the reactive group R 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 curable synthetic resin coating of the present invention, S is greater than 0.02.
According to another suitable curable synthetic resin coating of the present invention, r and S are equal to 0, and R
1And R
8It is the alkyl that contains acrylate.
If owing on the polymer molecule side chain is arranged, make reactive end Quito in the molecule in 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, can obtain high solidification rate 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, must in synthetic resin coating, add photoinitiator so.
In order in curable compound resin composition, to dissolve in the photoinitiator of capacity, must make (q+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 (phenyl) to exist.
If make synthetic resin coating contain 1 to 5%(weight) photoinitiator, the UV-light that can obtain suiting-curable synthetic resin coating so.
The preferred photoinitiator that is used for the synthetic resin coating of UV-light-curable is to be selected from 2,2-dimethoxy-2-phenyl-phenyl methyl ketone, 2,2-diethoxy-phenyl methyl ketone and 2, the coating in 2-dimethyl-2-hydroxyl-phenyl methyl ketone.
If synthetic resin coating contains one or more 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%(weight) one or more monomer acrylic compound.
The suitable monomer acrylic compound be select oneself omega-diol diacrylate, vinylformic acid 2-oxyethyl group-ethyl ester, vinylformic acid 2 '-compound in diethoxy-2-oxyethyl group-ethyl ester and the Viscoat 295.
According to another aspect of the present invention, the method that the present invention makes new synthetic resin coating comprises following steps:
A) preparation contains dichlorodimethylsilane, carboxylic acid and one or more are selected from the solution of the compound in dichloromethyl phenyl silane, dichloro diphenyl silane, two chloro-methyl hydrogen silane, a Chlorodimethyl hydrogen silane, trichloromethyl silane and the trichlorophenyl silane, selects the ratio of above-claimed cpd according to the desired composition that contains multipolymer.
B) alkanol of a great deal of is added in the solution, so that hydrolysis and polymerization to take place.
C) heated solution is till in fact hydrolysis is finished,
D) make high-molecular weight intermediate product and by product and separated from solvent with currently known methods,
E) dissolving high-molecular weight intermediate product, 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 solution,
J) heated solution till in fact reaction is finished, is got rid of the hydrogenchloride that is generated with known method,
K) with product and separation of by-products, and with known method purified product.
Below by reference embodiment and accompanying drawing, the present invention is done comparatively detailed explanation.
Fig. 1 represents the embodiment according to method of the present invention.
Fig. 2 a represents 2,2-methoxyl group-2-phenyl-phenyl methyl ketone.
Fig. 2 b represents 2,2-diethoxy-phenyl methyl ketone.
Fig. 2 c represents 2,2-dimethyl-2-hydroxyl-phenyl methyl ketone.
Fig. 3 a represents hexanediyl ester.
Fig. 3 b represents vinylformic acid 2-oxyethyl group-ethyl ester.
Fig. 3 c represent vinylformic acid 2 '-oxyethyl group-2-oxyethyl group-ethyl ester.
Fig. 3 d represents Viscoat 295.
The embodiment of the inventive method (Fig. 1).
With dichlorodimethylsilane (a), dichloromethyl phenyl silane (b) and a Chlorodimethyl hydrogen silane (c), the ratio in the composition that meets the desired multipolymer that obtains is dissolved in the acetate.Also can use other solution.In order to obtain desired response, must use carboxylic acid.Adopting acetate is to make polyreaction produce the polymer and the acyclic polysiloxane molecule of large portion as the benefit of solvent and reagent.For example, be 10000 polysiloxane for p=q=0.5 and molecular-weight average are provided, must be with 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, the methyl alcohol with a great deal of is added dropwise to solution on one side.Compare with other alkanols, adopt the advantage of methyl alcohol to be the by product of separating reaction generation at low temperatures.
Keep this solution under boiling state 2 hours, to be hydrolyzed and polymerization.Under 58 ℃ of temperature, fractionate out the methyl acetate that is generated, at 150 ℃ of temperature and pressure 2 * 10
4Fractionate out low molecule and rudimentary cyclosiloxane under the handkerchief.P/q ratio in the a/b ratio decision product.C/(a+b) molecular weight of ratio decision final product.
Except that above-mentioned silane, also available dichloro diphenyl silane.The diphenyl siloxane base is bonded in the polymkeric substance under the situation of using this silane, and institute is so that r is not equal to zero.Contain acrylate alkyl 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 consumption too conference 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 intermediate products are dissolved in, in the Anaesthetie Ether that 200 milliliters 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 is added dropwise to 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, Trimethylamine and the vinylformic acid muriate with a great deal of is added dropwise to solution on one side.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.It can alveolation imaging air sample bubble, by solution, take away the HCl that is generated.
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 to prolong under the situation of 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 come isolation of intermediate products and final product with extraction process, these certainly all within the scope of the present invention.
The example of the synthetic resin coating that the present invention is curable.
Multipolymer according to aforesaid method is made does not need to add any material again, just can be used as curable synthetic resin coating.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 4%(weight) 2, (Fig. 2 a) photoinitiator adds in the curable synthetic resin coating 2-dimethoxy-2-phenyl acetophenone, and it is possible solidifying with uv irradiation method.For example, can produce wavelength is that 200 to 400 millimicrons, the light intensity on synthetic resin coating are 0.5 watt/centimetre
2High pressure mercury vapour lamp be to be applicable to solidified.Solidify the composition that the required time depends on curable synthetic resin coating, generally below 5 seconds.
Table 1 has been enumerated some character that contains the curable synthetic resin coating of various ratio monomeric unit multipolymers of the present invention.Tg is the second-order transition temperature after the material cured, and material presents the temperature like rubber properties when promptly surpassing this temperature.n
25 DBe the refractive index of material in the time of 25 ℃ before solidifying.
Table 1
P Q S Tg（℃） 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.
Mn=14,000, the refractive index n of the curable synthetic resin coating of p=q=0.49 and S=0.02
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 coating presents Newtonian behavior.Described coating refractive index n of (as above-mentioned, with uviolizing 5 seconds) after curing
25 DBe 1.5030, second-order transition temperature Tg is-60 ℃, and 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 coreactions 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), vinylformic acid 2 '-oxyethyl group-2-oxyethyl group-ethyl ester (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 ultraviolet ray by means of above-mentioned lamp set time.
Table 2
HDDA EEEA TMPTA Tg set time n
25 D
%(weight) %(weight) %(weight) (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 the add-on of obvious raising hexanediyl ester or Viscoat 295, the speed of response surge.The addition of monomer acrylate increases to 20%(weight by 0), 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 400 meters as surface-area with the filler of routine in addition
2The SiO of/gram
2Add in the curable synthetic resin coating.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 coating of the present invention has high solidification rate, it is still stable before using, therefore can standing storage.If curable synthetic resin coating is used for the high-temperature material surface, its wettability also is good (not generating drop).In addition, above-mentioned synthetic resin coating also has more than second-order transition temperature with 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.
Claims (11)
1, a kind of curable synthetic resin coating of multipolymer that contains, the monomeric unit that wherein said multipolymer has comprises by dimethyl siloxane and at least a siloxanes that is selected from methylphenyl siloxane and the diphenyl siloxane, it is characterized in that multipolymer is a kind of compound of following formula:
In the formula: R
1And R
8Be to be selected from alkyl, aryl and to contain organic group in the alkyl of acrylate, R
2, R
3, R
4, R
6And R
7Be the organic group that is selected from alkyl and the aryl, R
5Be the organic group that contains acrylate, the molecular-weight average of polymkeric substance is 1,000 to 1,000, and between 000, the shared average score of various monomeric units is in following limited range 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 and monomeric unit wherein can block, alternately or random fashion is distributed in the molecule and each copolymer molecule wherein contain at least two acrylate-based.
2, according to the curable synthetic resin coating of claim 1, it is characterized in that R
5It is a kind of alkyl that contains acrylate.
3,, it is characterized in that S is greater than 0.02 according to the curable synthetic resin coating of claim 1.
4,, it is characterized in that r and S equal zero R according to the curable synthetic resin coating of claim 1
1And R
8For containing the alkyl of acrylate.
5, according to the curable synthetic resin coating of claim 1, it is characterized in that R
5Be with polymer molecule main chain homotype with the average polysiloxane chain of forming that contains acrylate.
6,, it is characterized in that (q+2r) is greater than 0.3 according to the curable synthetic resin coating of claim 1.
7,, it is characterized in that containing 1 to 5%(weight in the synthetic resin coating according to the curable synthetic resin coating of claim 6) photoinitiator.
8,, it is characterized in that photoinitiator is to be selected from 2,2-dimethoxy-2-phenyl-phenyl methyl ketone, 2,2-diethoxy phenyl methyl ketone and 2, the compound in 2-dimethyl-2-glycoloyl benzene according to the curable synthetic resin coating of claim 7.
9,, it is characterized in that synthetic resin coating contains 0 to 20%(weight according to the curable synthetic resin coating of claim 1 to 8) one or more monomer acrylic compound.
10, according to the curable synthetic resin coating of claim 9, it is characterized in that the monomer acrylic compound be select oneself omega-diol diacrylate, vinylformic acid 2-ethoxyethyl group ester, vinylformic acid 2 '-compound in oxyethyl group-2-ethoxyethyl group ester and the Viscoat 295.
11, the preparation method who contains the curable synthetic resin coating of multipolymer of claim 1, comprise the preparation method who contains by the multipolymer of dimethyl siloxane and at least a monomeric unit that is selected from the siloxanes in methylphenyl siloxane and the diphenyl siloxane, the method is characterized in that:
A) preparation contains dichlorodimethylsilane, carboxylic acid and one or more are selected from the solution of the compound in dichloromethyl phenyl silane, dichloro diphenyl silane, dichloro monomethyl hydrogen silane, a Chlorodimethyl hydrogen silane, trichloromethyl silane and the trichlorophenyl silane, select the ratio of above-claimed cpd according to the desired composition that contains multipolymer
B) alkanol of a great deal of is added in the solution, with generation hydrolysis and polymerization,
C) heated solution is till in fact hydrolysis is finished,
D) make high-molecular weight intermediate product and by product and separated from solvent with currently known methods,
E) dissolving high-molecular weight intermediate product, 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) with product and separation of by-products, 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 CN85101534A (en) | 1987-01-17 |
| CN1010319B true 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101027259B (en) * | 2004-09-28 | 2012-07-04 | 帝斯曼知识产权资产管理有限公司 | Radiation-curable liquid resin optical fiber upjacket composition |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3516543B2 (en) * | 1995-10-27 | 2004-04-05 | 株式会社小糸製作所 | Colored coating agent for turn signal lamp and turn signal lamp |
| US5891942A (en) * | 1997-05-01 | 1999-04-06 | Fibre Glass-Evercoat Company, Inc. | 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 |
| AU753296B2 (en) * | 1998-02-17 | 2002-10-17 | E.I. Du Pont De Nemours And Company | Method for producing powder coatings |
| DE102005008951A1 (en) * | 2005-02-24 | 2006-09-07 | Wacker Chemie Ag | Silicone rubber compositions and permanent load-resistant silicone elastomers obtained therefrom |
| FR2926082B1 (en) * | 2008-01-04 | 2010-01-15 | Nexans | PHOTORETICULABLE COMPOSITION COMPRISING A POLYORGANOSILOXANE. |
-
1985
- 1985-04-01 CN CN 85101534 patent/CN1010319B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101027259B (en) * | 2004-09-28 | 2012-07-04 | 帝斯曼知识产权资产管理有限公司 | Radiation-curable liquid resin optical fiber upjacket composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN85101534A (en) | 1987-01-17 |
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