CN102181013A - Flame-retardant heat-resistant unsaturated polyester-modified epoxy solvent-free resin - Google Patents
Flame-retardant heat-resistant unsaturated polyester-modified epoxy solvent-free resin Download PDFInfo
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- CN102181013A CN102181013A CN2011100718899A CN201110071889A CN102181013A CN 102181013 A CN102181013 A CN 102181013A CN 2011100718899 A CN2011100718899 A CN 2011100718899A CN 201110071889 A CN201110071889 A CN 201110071889A CN 102181013 A CN102181013 A CN 102181013A
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Abstract
The invention discloses flame-retardant heat-resistant unsaturated polyester-modified epoxy solvent-free resin which is suitable for soaking a dry-type transformer and mining electrical equipment. The solvent-free resin is characterized by comprising base unsaturated polyester, an unsaturated vinyl monomer, epoxy resin comprising two or more epoxy groups, an amine polymer, an amine epoxy curing agent and a flame retardant. Compared with unifunctional flame-retardant unsaturated polyester resin or epoxy resin, the flame-retardant heat-resistant unsaturated polyester-modified epoxy solvent-free resin has the characteristics that: a curing agent with flame retardance is used; and when being used separately, the curing agent is stored stably and has a latent function. When being used together with a catalyst with a promoting function, the solvent-free resin has high electrical property and mechanical property, and can be cured quickly at high temperature.
Description
Technical field
The invention belongs to the electric insulation resin technical field, particularly relate to a kind of flame retardant type heat resisting unsaturated polyester modified epoxy solventfree resin that is applicable to dry type transformer, mining electric installation dip treating.
Background technology
In thermoplastic resin, unsaturated polyester resin as polybutene terephthalate, styrene resin etc., all has good machinery, electric property, and the effect of waterproof, the anti-climate change of anti-chemical burn into.Present dry type transformer, especially mining electric installation requires the dipping solventfree resin that certain flame retardant resistance is arranged.Require temperature classification more than the H level, simultaneously good protection against the tide and rustless property will be arranged.Domestic existing solvent impregnated resin can't be realized this requirement, and some external technology are used halogen is added in the resin playing fire-retardant effect, but this series products can produce toxic gases such as discharging dioxin, and human body is had bigger harm.
Summary of the invention
In order to realize purpose of the present invention, the invention provides a kind of flame retardant type heat resisting unsaturated polyester modified epoxy solventfree resin, different with the unsaturated polyester resin with flame retardant resistance or the Resins, epoxy of independent function, be to use solidifying agent with anti-flaming function, when this solidifying agent uses separately, store very stablely, have the class incubation function.When it uses simultaneously with the catalyzer with promotion function, possess good electrical properties and mechanical property, can implement rapid curing molding under the high temperature simultaneously again.
In order to achieve the above object, the technical solution used in the present invention is:
A kind of flame retardant type heat resisting unsaturated polyester modified epoxy solventfree resin, it is characterized in that: comprise basic unsaturated polyester, unsaturated ethylene base class monomer, the Resins, epoxy that includes the epoxide group more than 2 or 2, amine polymer, amine epoxy hardener, fire retardant;
The structural formula of described basic unsaturated polyester is:
[-O-POR1-CH2CHR2-COO-]
Wherein R1 has branch or branchiess 1 to 18 alkyl, cycloalkyl, aryl, the alkylaryl of having, and R2 is methyl or hydrogen;
The mass ratio of described each composition is as follows:
Composition quality proportion of composing (%)
Basis unsaturated polyester 25%-50%
Unsaturated ethylene base class monomer 0.8%-1.5%
The Resins, epoxy 8%-20% that includes the epoxide group more than 2 or 2
Amine polymer 10%-40%
Amine epoxy hardener 0.1%-8%
Fire retardant 5%-10%
Aforesaid a kind of flame retardant type heat resisting unsaturated polyester modified epoxy solventfree resin is characterized in that:
The quality optimization of described each composition is such as following:
Composition quality proportion of composing (%)
Basis unsaturated polyester 30%-45%
Unsaturated ethylene base class monomer 1%-1.2%
The Resins, epoxy 10%-15% that includes the epoxide group more than 2 or 2
Amine polymer 17%-35%
Amine epoxy hardener 0.5%-6%
Fire retardant 5%-10%
Aforesaid a kind of flame retardant type heat resisting unsaturated polyester modified epoxy solventfree resin, it is characterized in that: described fire retardant comprises following several composition: the acid of brominated or chlorine or alcohol cpd, phosphorus ester, nitrogen annular compound.
Aforesaid a kind of flame retardant type heat resisting unsaturated polyester modified epoxy solventfree resin, it is characterized in that: described basic unsaturated polyester solidifies by styrene monomer, and styrene monomer solidified ratio is 25%-40% of a unsaturated polyester.
Aforesaid a kind of flame retardant type heat resisting unsaturated polyester modified epoxy solventfree resin, it is characterized in that: the described Resins, epoxy that includes the epoxide group more than 2 or 2 comprises following several composition: butylglycidyl ether, Styrene oxide 98min., phenyl glycidyl ether, polyhydroxy polycarboxylic glycerol ether.
Aforesaid a kind of flame retardant type heat resisting unsaturated polyester modified epoxy solventfree resin is characterized in that: described amine polymer can adopt a kind of of amine polyethers, amine diene hydrogenation polyethers, polyolefin polymer.
Aforesaid a kind of flame retardant type heat resisting unsaturated polyester modified epoxy solventfree resin, it is characterized in that: described basic unsaturated polyester contains low-molecular-weight glycol, and glycol contains 2 to 12 carbon atoms.
Aforesaid a kind of flame retardant type heat resisting unsaturated polyester modified epoxy solventfree resin, it is characterized in that: described low-molecular-weight glycol is 1,2-propyleneglycoles, 1,3-propyleneglycoles, 3,4-glycol ether, 1,2-propylene glycol, 1,4-butyleneglycol, neopentyl glycol.
The invention has the beneficial effects as follows:
The flame retardant properties of resin system of the present invention is that multi-functional resins adds solidifying agent and implements, and has avoided the expensive and complicated synthesis technique of simple property flame retardant type unsaturated polyester or Resins, epoxy.Finally reach the equal result who gets with simple property flame retardant polyester or epoxy, the strong point of bringing is to have guaranteed thermotolerance, moistureproofness and sticking epistasis, can utilize preferably in professional dry type transformer and use.In addition, by epoxide modified, as in unsaturated polyester, adding amine epoxy, the crosslinked ability of unsaturated polyester resin be improved, and then strengthened toughness and anti-fracture energy.
Embodiment
Below in conjunction with specific embodiment, describe the specific embodiment of the present invention in detail:
Below providing 3 examples, is composition with unsaturated polyester (ET-80), unsaturated monomer (Styrene), Resins, epoxy (Epon 828) and amine polymer (Hycar 1300X16, Ancamine K61B):
Embodiment 1
Step: A. is the maleic acid anhydrides of following 107 grams, and the echothiophate compounds of 147 grams, 1 of 184 grams, 2-propylene glycol, the Resorcinol of the dimethylbenzene of 100 grams and 0.1 gram add nitrogen and mix to stir also and heated 2 hours under 100 ° of C.
B. above-mentioned A gained was warming up to 150 ° of C 5 hours, this reaction is thermopositive reaction.
C. the phosphorus compound that above-mentioned B gained is added weight resin 8.6%.
D. the vinylbenzene that above-mentioned C gained is added weight 35%.
Embodiment 2
Step: A. is with the maleic acid anhydrides of 107 grams, the phthalic acid of 81 grams, the echothiophate compound of 74 grams, 1 of 184 grams, the 2-propylene glycol, the Resorcinol of 100 gram dimethylbenzene and 0.1 gram adds nitrogen mixing stirring and heated 2 hours under 160 ° of C.
B. above-mentioned A reaction is thermopositive reaction, after heat release stops, above-mentioned gained is heated to 180 ° of C 5 hours.
C. the phosphorus compound that above-mentioned B gained is added weight resin 8.6%.
D. above-mentioned B gained is added 35% vinylbenzene.
Embodiment 3
Step: A. is with the maleic acid anhydrides of 72 grams, the phthalic acid of 81 grams, the echothiophate compound of 74 grams, 1 of 184 grams, the 2-propylene glycol, 100 restrain the Resorcinol of dimethylbenzene and 0.1 gram, and Epon 828 40 grams mix stirring with Hycar 1,300,X16 52 gram adding nitrogen and heated 2 hours under 160 ° of C.
B. above-mentioned A reaction is thermopositive reaction, after heat release stops, above-mentioned gained is heated to 180 ° of C 5 hours.
C. the phosphorus compound that above-mentioned B gained is added weight resin 8.6%.
D. above-mentioned B gained is added 35% vinylbenzene.
In the various embodiments described above, actual flame retardant effect is as follows: 50w horizontal burning test HB40 level
50w testing vertical flammability V-0 level
Oxygen index 33.5
More than show and described ultimate principle of the present invention, principal character and advantage.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in the foregoing description and the specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is by appending claims and equivalent circle thereof.
Claims (8)
1. flame retardant type heat resisting unsaturated polyester modified epoxy solventfree resin, it is characterized in that: comprise basic unsaturated polyester, unsaturated ethylene base class monomer, the Resins, epoxy that includes the epoxide group more than 2 or 2, amine polymer, amine epoxy hardener, fire retardant;
The structural formula of described basic unsaturated polyester is:
[-O-POR1-CH2CHR2-COO-]
Wherein R1 has branch or branchiess 1 to 18 alkyl, cycloalkyl, aryl, the alkylaryl of having, and R2 is methyl or hydrogen;
The mass ratio of described each composition is as follows:
Composition quality proportion of composing (%)
Basis unsaturated polyester 25%-50%
Unsaturated ethylene base class monomer 0.8%-1.5%
The Resins, epoxy 8%-20% that includes the epoxide group more than 2 or 2
Amine polymer 10%-40%
Amine epoxy hardener 0.1%-8%
Fire retardant 5%-10%.
2. a kind of flame retardant type heat resisting unsaturated polyester modified epoxy solventfree resin according to claim 1 is characterized in that:
The quality optimization of described each composition is such as following:
Composition quality proportion of composing (%)
Basis unsaturated polyester 30%-45%
Unsaturated ethylene base class monomer 1%-1.2%
The Resins, epoxy 10%-15% that includes the epoxide group more than 2 or 2
Amine polymer 17%-35%
Amine epoxy hardener 0.5%-6%
Fire retardant 5%-10%.
3. a kind of flame retardant type heat resisting unsaturated polyester modified epoxy solventfree resin according to claim 1 and 2, it is characterized in that: described fire retardant comprises following several composition: the acid of brominated or chlorine or alcohol cpd, phosphorus ester, nitrogen annular compound.
4. a kind of flame retardant type heat resisting unsaturated polyester modified epoxy solventfree resin according to claim 3, it is characterized in that: described basic unsaturated polyester solidifies by styrene monomer, and styrene monomer solidified ratio is 25%-40% of a unsaturated polyester.
5. a kind of flame retardant type heat resisting unsaturated polyester modified epoxy solventfree resin according to claim 4, it is characterized in that: the described Resins, epoxy that includes the epoxide group more than 2 or 2 comprises following several composition: butylglycidyl ether, Styrene oxide 98min., phenyl glycidyl ether, polyhydroxy polycarboxylic glycerol ether.
6. a kind of flame retardant type heat resisting unsaturated polyester modified epoxy solventfree resin according to claim 5 is characterized in that: described amine polymer can adopt a kind of of amine polyethers, amine diene hydrogenation polyethers, polyolefin polymer.
7. a kind of flame retardant type heat resisting unsaturated polyester modified epoxy solventfree resin according to claim 6, it is characterized in that: described basic unsaturated polyester contains low-molecular-weight glycol, and glycol contains 2 to 12 carbon atoms.
8. a kind of flame retardant type heat resisting unsaturated polyester modified epoxy solventfree resin according to claim 7, it is characterized in that: described low-molecular-weight glycol is 1,2-propyleneglycoles, 1,3-propyleneglycoles, 3,4-glycol ether, 1,2-propylene glycol, 1,4-butyleneglycol, neopentyl glycol.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100718899A CN102181013A (en) | 2011-03-23 | 2011-03-23 | Flame-retardant heat-resistant unsaturated polyester-modified epoxy solvent-free resin |
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| CN2011100718899A CN102181013A (en) | 2011-03-23 | 2011-03-23 | Flame-retardant heat-resistant unsaturated polyester-modified epoxy solvent-free resin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130964A (en) * | 2013-02-01 | 2013-06-05 | 海宁永大电气新材料有限公司 | Solvent-free impregnating resin for low voltage motor and medium voltage motor and solidification method |
| CN103304745A (en) * | 2013-06-21 | 2013-09-18 | 浙江荣泰科技企业有限公司 | Polymerizable flame retardant resin |
-
2011
- 2011-03-23 CN CN2011100718899A patent/CN102181013A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130964A (en) * | 2013-02-01 | 2013-06-05 | 海宁永大电气新材料有限公司 | Solvent-free impregnating resin for low voltage motor and medium voltage motor and solidification method |
| CN103130964B (en) * | 2013-02-01 | 2016-04-13 | 海宁永大电气新材料有限公司 | Low, Medium-voltage motor solvent-free impregnating resin and curing |
| CN103304745A (en) * | 2013-06-21 | 2013-09-18 | 浙江荣泰科技企业有限公司 | Polymerizable flame retardant resin |
| CN103304745B (en) * | 2013-06-21 | 2015-04-08 | 浙江荣泰科技企业有限公司 | Polymerizable flame retardant resin |
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Application publication date: 20110914 |