CN1962712A - Single component solid oxirene resin - Google Patents
Single component solid oxirene resin Download PDFInfo
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- CN1962712A CN1962712A CN 200610118975 CN200610118975A CN1962712A CN 1962712 A CN1962712 A CN 1962712A CN 200610118975 CN200610118975 CN 200610118975 CN 200610118975 A CN200610118975 A CN 200610118975A CN 1962712 A CN1962712 A CN 1962712A
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- epoxy
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- vinyl resin
- epoxy vinyl
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- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a single-component solid epoxy ethylene resin, which comprises the following parts: 80-92% base resin, 1-10% isocyanate, 1-7% phthalandione dialkylene ester and 1-3% peroxy initiator, wherein the base resin is reacted by epoxy resin E-12 or epoxy resin E-20 with methyl acroleic acid through ringopening and esterifying; the isocyanate is bifunctional diisocyanate.
Description
Technical field
The present invention relates to a kind of epoxy vinyl resin, specifically, relate to a kind of single component solid oxirene resin.
Background technology
The epoxy vinyl resin is meant: Resins, epoxy is through the resin of unsaturated organic monocarboxylic acid modification (carrying out the esterification by ring opening reaction by unsaturated organic monocarboxylic acid and Resins, epoxy) gained, and it is widely used in fields such as chemical industry, metallurgy and automobile making.
Existing epoxy vinyl resin mostly is the liquid epoxy vinyl resin of two components greatly, people such as Qian Zhiyin (patent CN1590426A) obtain good than the #3201 Vinylite modified product of a kind of erosion resistance, thermotolerance, mechanical property by isocyanate-modified vinyl base resin, epoxy vinyl resin after the modification has good resistance to acids and bases, its heat-drawn wire is 109 ℃, improved 9 ℃ than the matrix Vinylite before the modification, the little and product of increase rate is liquid.People such as Chih-hsiung Huang (patent CN 1544491A) obtain the epoxy vinyl resin by bisphenol f type epoxy resin is carried out modification, the thermal change type temperature of modified resin has compared with the raising of bisphenol A-type modification a lot, reach nearly 200 ℃, its shortcoming is that the used F-51 type of patent Resins, epoxy is raw material, the epoxy vinyl resin that obtains is liquid, be unfavorable for that transportation stores, and is not suitable for use in powder coating.Patent CN1640979A discloses a kind of two component fast speed solidified epoxy adhesive, forms the A component by Resins, epoxy or modified epoxy (epoxy vinyl resin), softening agent or toughner; Constitute the B component by modified amine curing agent, compound accelerant, coupling agent, at room temperature can PhastGel, reach the use standard after for some time, adjuvant used a lot of and be two components in this patent, complex procedures need be carried out mix during use in proportion.The material that mixes must use at the appointed time, and unnecessary material can't utilize once more, and this can cause the rising of material waste and use cost.
Because the liquid epoxy vinyl resin of these pairs component not only exists storage, transportation and uses the defective of difficulty, and also has longer drawback set time, patent CN1640979A discloses a kind of two component fast speed solidified epoxy adhesive, forms the A component by Resins, epoxy or modified epoxy, softening agent or toughner; Constitute the B component by modified amine curing agent, compound accelerant, coupling agent, at room temperature 3～8 minutes gels reach the use standard after 30 minutes, and wherein the solidifying and setting time longly needs half an hour.Above-mentioned shortcoming causes the liquid epoxy vinyl resins of existing two components can't satisfy some fast and the requirement of the production technique of serialization, thereby has limited the Application Areas of epoxy vinyl resin.
Given this, this area presses for that research and development a kind ofly not only are convenient to store, transportation and using, and set time, short epoxy vinyl resin satisfied the demand of production department.
Summary of the invention
The objective of the invention is to, provide a kind of and be convenient to store, transportation and using, and set time short epoxy vinyl resin, overcome the defective that exists in the prior art.
The said epoxy vinyl resin of the present invention is a single component solid oxirene resin, and by percentage to the quality, it comprises following component:
Matrix resin 80%～92%
Isocyanic ester 1%～10%
Diallyl phthalate 1%～7%
Peroxide initiator 1%～3%
Wherein: said matrix resin carries out esterification by ring opening by solid epoxies such as Resins, epoxy E-12 (by the name of the nomenclature of GB GB/T1630-1989, down with) or Resins, epoxy E-20 and methyl-prop diluted acid monomer and reacts and make; Said isocyanic ester is bifunctional vulcabond (recommending to use tolylene diisocyanate or 4,4 '-diphenylmethanediisocyanate); Preferred dicumyl peroxide of said peroxide initiator (DCP) or peroxidized t-butyl perbenzoate (TBPB).
The preferred following preparation method's preparation of the said matrix resin of the present invention:
Resins, epoxy E-12 or E-20 are melted, under 130 ℃～145 ℃ conditions, in Resins, epoxy E-12 that has melted or E-20, add catalyzer and stopper, catalyst consumption is 0.2g/100g Resins, epoxy E-12 or E-20, the consumption of stopper is 0.1g/100g Resins, epoxy E-12 or E-20, again to this reaction system (by the Resins, epoxy E-12 or the E-20 that have melted, stopper and catalyzer are formed) the middle methacrylic acid monomer that adds, finish, obtain target compound (the said matrix resin of the present invention) after 1～2.5 hour in 130 ℃～145 ℃ stirrings (stirring velocity is advisable with 500～800rpm).
Wherein: the mol ratio of Resins, epoxy E-12 or Resins, epoxy E-20 and methacrylic acid monomer is 1: 1.1; Said stopper is a phenolic compound, and the stopper that the present invention recommends to use is Resorcinol or Resorcinol; Said catalyzer is a quaternary ammonium salt compound, and it has structure shown in the formula (1):
Formula (1) R
1, R
2, R
3, R
4Be selected from C respectively
1～C
6A kind of in the alkyl, X is a halogen; Preferred R
1, R
2, R
3, R
4Be selected from C respectively
1～C
4A kind of in the alkyl, X is Cl or Br.Best catalyzer is 4 bromide or Tetrabutyl amonium bromide.
In addition, in reaction process, the time that drips methacrylic acid monomer should be controlled within 30～60 minutes.Methacrylic acid monomer drips too soon then it and epoxy group(ing) has little time to carry out esterification, thereby generates a large amount of homopolymer; Otherwise, then can prolong the reaction times, cause the product color burn.
The method for preparing the said epoxy vinyl resin of the present invention, its key step is: the matrix resin that will make as stated above (vacuum-drying: drying temperature is 80 ℃, at least 12 hours time of drying) after water washing (purpose is eccysis residual monomer and polymethyl acrylic acid homopolymer) and drying is pressed the described mixed of preamble with isocyanic ester, diallyl phthalate and peroxy initiator and is evenly got final product.
Compared with prior art, the present invention has following advantage:
(1) storage, transportation and the use of the said epoxy vinyl resin of invention are all very convenient;
(2) the said epoxy vinyl resin of invention can fast setting (180 ℃ time, be 2～3 minutes set time);
(3) has higher heat-drawn wire (reaching as high as nearly 120 ℃) behind the said epoxy vinyl resin solidification of invention.
Embodiment
The present invention is further elaborated below by embodiment, and its purpose only is better to understand content of the present invention and unrestricted protection scope of the present invention:
The preparation of matrix resin:
Embodiment 1
In the there-necked flask that dropping funnel, electric mixer and prolong are housed, add 20g Resins, epoxy E-12, about 140 ℃ of following preheating 1h, after treating that Resins, epoxy melts fully, add 0.04g Tetrabutyl amonium bromide (catalyzer), and drip the methacrylic acid 2.4g that is dissolved with 0.02g Resorcinol (stopper), begin simultaneously to stir, stirring velocity is 800rpm, methacrylic acid dropwised in 30 minutes, continue reaction finished in 1.5 hours, it is yellow that product is, and reactivity (referring to participate in the epoxy group(ing) per-cent of reaction) is 96.8%.Take out the reactant oven dry and be crushed into powder, then with the warm water washing, monomer-free and homopolymer characteristic peak are put into vacuum drying oven again in the washing lotion infrared spectrum, in 80 ℃ of dryings 12 hours, the light yellow product of solid state.
Embodiment 2
In the there-necked flask that dropping funnel, electric mixer and prolong are housed, add 20g Resins, epoxy E-12, about 145 ℃ of following preheating 1h of melt temperature, after treating that Resins, epoxy melts fully, add 0.04g tetrabutylammonium chloride (catalyzer), and drip the methacrylic acid 2.4g that is dissolved with 0.02g Resorcinol (stopper), begin simultaneously to stir, stirring velocity is 800rpm, methacrylic acid dropwised in 30 minutes, continue reaction finished in 2 hours, product is brown, and reactivity (being meant the per-cent that participates in reaction in the epoxy group(ing)) is 79.8%.Take out the reactant oven dry and be crushed into powder, then with the warm water washing, monomer-free and homopolymer characteristic peak are put into vacuum drying oven again in the washing lotion infrared spectrum, in 80 ℃ of dryings 12 hours, the solid brown product.
Embodiment 3
In the there-necked flask that dropping funnel, electric mixer and prolong are housed, add 20g Resins, epoxy E-20, about 130 ℃ of following preheating 1h of melt temperature, after treating that Resins, epoxy melts fully, add 0.04g 4 bromide (catalyzer), and drip the methacrylic acid 2.4g that is dissolved with 0.02g Resorcinol (stopper), begin simultaneously to stir, stirring velocity is 800rpm, methacrylic acid dropwised in 30 minutes, continue reaction finished in 1 hour, product is khaki color, and reactivity (being meant the per-cent that participates in reaction in the epoxy group(ing)) is 67.9%.Take out the reactant oven dry and be crushed into powder, then with warm water it is washed, monomer-free and homopolymer characteristic peak in the washing lotion infrared spectrum are put into vacuum drying oven again in 80 ℃ of dryings 12 hours, obtain the solid yellow product.
The preparation of single component solid oxirene resin:
Embodiment 4
Matrix resin, MDI (MDI), diallyl phthalate (DAP) and the dicumyl peroxide (DCP) that will be made by embodiment 1 by following mixed evenly and be crushed into powder promptly gets the single component solid oxirene resin product.
Matrix resin 92wt%
MDI 1wt％
DAP 5wt％
DCP 2wt％
Gained single component solid oxirene resin product is in room temperature (20 ℃～30 ℃) not conglomeration of prolonged preservation; It solidifies in 3 minutes in the time of 180 ℃, and the Vicat softening point of cured article is that 115.5 ℃, shock strength are 90J/m
2
Embodiment 5
Matrix resin, MDI (MDI), diallyl phthalate (DAP) and the dicumyl peroxide (DCP) that will be made by embodiment 1 by following mixed evenly and be crushed into powder promptly gets the single component solid oxirene resin product.
Matrix resin 90wt%
MDI 3wt％
DAP 5wt％
DCP 2wt％
Gained single component solid oxirene resin product is in room temperature (20 ℃～30 ℃) not conglomeration of prolonged preservation; They are in the time of 180 ℃, and be 2.5 minutes set time, and the Vicat softening point of gained cured article is that 107.1 ℃, shock strength are 110J/m
2
Claims (7)
1, a kind of epoxy vinyl resin is characterized in that, said epoxy vinyl resin is a single component solid oxirene resin, and by percentage to the quality, it comprises following component:
Matrix resin 80%～92%
Isocyanic ester 1%～10%
Diallyl phthalate 1%～7%
Peroxide initiator 1%～3%
Wherein: said matrix resin carries out the esterification by ring opening reaction by Resins, epoxy E-12 or Resins, epoxy E-20 and methyl-prop diluted acid monomer and makes; Said isocyanic ester is the bifunctional vulcabond.
As the said epoxy vinyl resin of claim 1, it is characterized in that 2, wherein said isocyanic ester is tolylene diisocyanate or 4,4 '-diphenylmethanediisocyanate.
As the said epoxy vinyl resin of claim 1, it is characterized in that 3, wherein said peroxide initiator is dicumyl peroxide or peroxidized t-butyl perbenzoate.
4, as any said epoxy vinyl resin in the claim 1～3, it is characterized in that wherein used matrix resin prepares by the following method:
Resins, epoxy E-12 or E-20 are melted, under 130 ℃～145 ℃ conditions, in Resins, epoxy E-12 that has melted or E-20, add catalyzer and stopper, catalyst consumption is 0.2g/100g Resins, epoxy E-12 or E-20, the consumption of stopper is 0.1g/100g Resins, epoxy E-12 or E-20, in this reaction system, add methacrylic acid monomer again, finish, obtain target compound after 1～2.5 hour in 130 ℃～145 ℃ stirrings;
Wherein: the mol ratio of Resins, epoxy E-12 or Resins, epoxy E-20 and methacrylic acid monomer is 1: 1.1, and said stopper is a phenolic compound, and said catalyzer is a quaternary ammonium salt compound, and it has structure shown in the formula (1):
R in the formula (1)
1, R
2, R
3, R
4Be selected from C respectively
1～C
6A kind of in the alkyl, X is a halogen.
As the said epoxy vinyl resin of claim 4, it is characterized in that 5, wherein said stopper is Resorcinol or Resorcinol.
6, as the said epoxy vinyl resin of claim 4, it is characterized in that, wherein R
1, R
2, R
3, R
4Be selected from C respectively
1～C
4A kind of in the alkyl, X is Cl or Br.
As the said epoxy vinyl resin of claim 4, it is characterized in that 7, wherein the reinforced time of methacrylic acid monomer was controlled at 30～60 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610118975XA CN100497431C (en) | 2006-12-01 | 2006-12-01 | Single component solid oxirene resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610118975XA CN100497431C (en) | 2006-12-01 | 2006-12-01 | Single component solid oxirene resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1962712A true CN1962712A (en) | 2007-05-16 |
| CN100497431C CN100497431C (en) | 2009-06-10 |
Family
ID=38081954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200610118975XA Expired - Fee Related CN100497431C (en) | 2006-12-01 | 2006-12-01 | Single component solid oxirene resin |
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| Country | Link |
|---|---|
| CN (1) | CN100497431C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111116857A (en) * | 2020-01-06 | 2020-05-08 | 华东理工大学华昌聚合物有限公司 | Vinyl resin and preparation method thereof |
-
2006
- 2006-12-01 CN CNB200610118975XA patent/CN100497431C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111116857A (en) * | 2020-01-06 | 2020-05-08 | 华东理工大学华昌聚合物有限公司 | Vinyl resin and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN100497431C (en) | 2009-06-10 |
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Granted publication date: 20090610 Termination date: 20111201 |