CN104031213B - A kind of low smoke and zero halogen heat-resistant fireproof vinyl ester resin and preparation method thereof - Google Patents
A kind of low smoke and zero halogen heat-resistant fireproof vinyl ester resin and preparation method thereof Download PDFInfo
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- CN104031213B CN104031213B CN201410238091.2A CN201410238091A CN104031213B CN 104031213 B CN104031213 B CN 104031213B CN 201410238091 A CN201410238091 A CN 201410238091A CN 104031213 B CN104031213 B CN 104031213B
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Abstract
The present invention relates to a kind of low smoke and zero halogen heat-resistant fireproof vinyl ester resin and preparation method thereof, belong to flame-proof ethylene base ester resin technology field.It is prepared through series reaction by materials such as epoxy resin, unsaturated monoacid, reactive flame retardant, additive flame retardant, catalyst, polymerization inhibitor and crosslinkable monomers.The present invention is made up of the relatively low raw material of price, and preparation cost is low, and association reaction type and the resultant effect of two kinds of fire retardants of addition type, flame retardant effect is better than like product on market；This flame-retarded resin low smoke and zero halogen, it is possible to substitute the brominated flame retardant chemical modification vinylite that there is halogen environmental issue；And modest viscosity, having good workability, anti-settling performance is good, has prominent corrosion-resistant and heat-resisting quantity, can be used for construction material, automotive part etc., is particularly well-suited to the fibre glass product manufacture of the low-smoke non-halogen flame-retardant requirements such as hand pasting forming passenger train parts.
Description
Technical field
The present invention relates to flame-proof ethylene base ester resin, particularly to a kind of low smoke and zero halogen heat-resistant fireproof vinyl ester resin and
Preparation method.
Background technology
Being introduced by novolac epoxy resin in the skeleton of vinylester resin, the vinyl ester resin of synthesis is commonly referred to as phenol aldehyde type vinyl esters
Resin.Resin has higher heat stability.After resin solidification, crosslink density is big.Its heat distortion temperature reaches 140-160 DEG C,
Can increase the service life and have excellent corrosion resistance, especially to containing solutions of chlorine or organic solvent good corrosion resistance.In order to suitable
Answer the needs of high temperature strength situation, more producer that phenol formaldehyde epoxy vinyl ester resin has been carried out modification, improve the friendship of resin
Connection density and heat resistance, have excellent acidproof, solvent resistant corrosivity and antioxygenic property, it is adaptable to various high temperature strong corrosion
Situation, such as desulfurizer (FGD), high temperature stacks etc..
When running into the composite and antiseptic project that there are flame-retardancy requirements, the solution in current industry mostly is as follows: (1) leads to
Cross physical blending, additive flame retardant is scattered in macromolecular material with physical dispersion state, thus plays fire retardation；(2)
By chemical modification, ignition-proof element on the raw band of reaction will be participated in, participate in reaction by polymerization process, thus be attached to
In the main chain of high polymer or side chain, play fire retardation.The feature of reactive flame retardant is fire-retardant good stability, is difficult to disappear,
Impact on material is less, but operation and processing technique are complex.Additive flame retardant usage amount is big, operates more convenient,
It it is a kind of flame retardant series being widely adopted.At present, on market, a large amount of halogen-containing flame-retarded resins of response type used are low with Halogen
The environmental protection flame retardant technology of cigarette is incompatible, and single physical blending has pair to the physical property after resin solidification and decay resistance
Effect.
Chinese invention patent application CN201310624114.9, entitled a kind of Low-cost halogen-free chemical flame-retardant vinyl ester resin
And preparation method thereof.The component disclosing this flame-retardant vinyl ester resin includes bisphenol A type epoxy resin, phosphoric acid, unsaturation
Monocarboxylic acid, catalyst, polymerization inhibitor, crosslinkable monomers.Preparation method include charging, intensification, progressively intensification, insulation reaction,
Heat up again, cool down, stir the steps such as cooling.Complicated process of preparation, operates the easiest.
In view of this, develop a kind of preparation technology low smoke, zero halogen simple, in hgher efficiency resistant to elevated temperatures flame-proof ethylene base ester resin and
A combination thereof thing is the most significant.
Summary of the invention
It is an object of the invention to: solve the deficiency of existing low smoke and zero halogen heat-resistant fireproof vinyl ester resin, it is provided that a kind of low cigarette
Non-halogen flame-proof ethylene base ester resin and preparation method thereof.It effectively solves present flame-proof ethylene base ester resin art and generally exists not
The series of problems such as environmental protection, bad, the unstable complicated process of preparation of flame retardant effect.
The technical scheme realizing the object of the invention is: a kind of low smoke and zero halogen heat-resistant fireproof vinyl ester resin, including following quality
Each component of percentage ratio:
Described epoxy resin is epoxy novolac or o-cresol aldehyde epoxy；
The mass percent summation of described each component is 100%.
Above-mentioned low smoke and zero halogen heat-resistant fireproof vinyl ester resin, preferably includes each component of following mass percent:
Described for low smoke and zero halogen heat-resistant fireproof vinyl ester resin, described epoxy resin is epoxy novolac, o-cresol
One in aldehyde epoxy.
Described for low smoke and zero halogen heat-resistant fireproof vinyl ester resin, described unsaturated monocarboxylic acid be methacrylic acid,
One in acrylic acid, butenoic acid.
Described for low smoke and zero halogen heat-resistant fireproof vinyl ester resin, described polymerization inhibitor is hydroquinone, benzoquinone, tertiary fourth
One in base catechol.
Described for low smoke and zero halogen heat-resistant fireproof vinyl ester resin, described described catalyst be tetramethyl ammonia chloride, three
One, the quality of catalyst in ethanolamine, m-diaminobenzene., benzyltriethylammoinium chloride, N, accelerine, triphenyl phosphorus
Percentage ratio preferably 0.16%, 0.27%, 0.22%.
Described for the high temperature resistant vinyl ester resin of low smoke and zero halogen, described crosslinkable monomers is styrene and or methacrylic acid
Methyl ester.
Described for the high temperature resistant vinyl ester resin of low smoke and zero halogen, described reactive flame retardant be 2-carboxyethyl phenyl hypophosphorous acid,
One in tetra methylol hydroxide phosphine or phosphonate oligomers, reactive flame retardant preferred mass percentage ratio is 4.4%, 5.4%,
6.5%.
Described for the high temperature resistant vinyl ester resin of low smoke and zero halogen, described additive flame retardant be aluminium hydroxide, acid boron zinc or
One in magnesium hydroxide, additive flame retardant preferred mass percentage ratio is 33.3%, 21.8%, 24%.
Catalyst used by the present invention, catalytic efficiency is high, shortens the response time, improves production efficiency, and do not affect product
The long-term preservation of product, and preferentially determine the true scope of catalyst charge, further ensure catalytic efficiency, it is ensured that anti-
Answer effect.
The high temperature resistant vinyl ester resin of low smoke and zero halogen that present invention process is produced has corrosion-resistant and heat-resisting quantity, can be used for building
Build material, automotive part etc., be particularly well-suited to the fibre glass product manufacture of the low-smoke non-halogen flame-retardant requirements such as hand pasting forming passenger train parts.
The good effect that the present invention has: (1) is made up of the raw material that price is relatively low, and preparation cost is low；(2) association reaction type and adding
Adding the resultant effect of two kinds of fire retardants of type, flame retardant effect is better than market like product；(3) product do not contain halogen, low-smoke low-toxicity,
Heat-resisting, modest viscosity, have good workability, the design of anti-settling performance good (4) formula precisely, maximizes and embodies the collaborative of each component
Effect so that the vinyl ester resin of preparation has heat resistance and fire resistance.(5) this flame-retarded resin modest viscosity, construction
Performance is good, and anti-settling performance is good；(6) this resin has corrosion-resistant and heat-resisting quantity, can be used for construction material, automotive part etc.,
It is particularly well-suited to the fibre glass product manufacture of the low-smoke non-halogen flame-retardant requirements such as hand pasting forming passenger train parts
Detailed description of the invention
(embodiment 1)
Each component is weighed by following quality:
Raw material A, B, C, D, E are put into reactor, at 110 DEG C, reacts 4 hours, be then dissolved in F, be down to room
Add G after temperature to stir, airtight preservation.
(embodiment 2)
Raw material A, B, C, D, E are put into reactor, at 120 DEG C, reacts 2 hours, be then dissolved in F, be down to
Add G after room temperature to stir, airtight preservation.
(embodiment 3)
Raw material A, B, C, D, E are put into reactor, at 100 DEG C, reacts 5 hours, be then dissolved in F, be down to
Add G after room temperature to stir, airtight preservation.
(embodiment 4)
Raw material A, B, C, D, E are put into reactor, at 100 DEG C, reacts 5 hours, be then dissolved in F, be down to
Add G after room temperature to stir, airtight preservation.
(embodiment 5)
Raw material A, B, C, D, E are put into reactor, at 100 DEG C, reacts 5 hours, be then dissolved in F, be down to
Add G after room temperature to stir, airtight preservation.
(embodiment 6)
Each component is weighed by following quality:
Raw material A, B, C, D, E are put into reactor, at 110 DEG C, reacts 4 hours, be then dissolved in F, be down to room
Add G after temperature to stir, airtight preservation.
The fire-retardant combination that various embodiments above obtains makes fiberglass by standard GB/T/T8237, and lamination structure is 9 layer 0.4
Alkali-free woven roving, cure system: accelerator 0.6%/Naph2%, firming agent AKZO M-50
2%.Fiberglass post curing treatment: 100 DEG C × 3h+150 DEG C × 1h.25 DEG C of characteristics are as follows:
Making 2 comparative examples referring concurrently to prior art, comparative example 1 only adds reactive flame retardant, and comparative example 2 only adds and adds
Add type fire retardant, one-tenth glass fiber reinforced plastics product fabricated as described above.
Particular embodiments described above, is further described the purpose of the present invention, technical scheme and beneficial effect,
Be it should be understood that the specific embodiment that the foregoing is only the present invention, be not limited to the present invention, all in the present invention
Spirit and principle within, any modification, equivalent substitution and improvement etc. done, should be included in protection scope of the present invention it
In.
Claims (7)
1. a low smoke and zero halogen heat-resistant fireproof vinyl ester resin, it is characterised in that include each component of following mass percent:
Described epoxy resin is epoxy novolac or o-cresol aldehyde epoxy；
Described reactive flame retardant is the one in 2-carboxyethyl phenyl hypophosphorous acid, tetra methylol hydroxide phosphine or 9,10-dihydro-9-oxy miscellaneous-10-phospho hetero phenanthrene-10-oxide；
Described additive flame retardant is the one in aluminium hydroxide, Firebrake ZB or magnesium hydroxide；
The mass percent summation of described each component is 100%.
Low smoke and zero halogen heat-resistant fireproof vinyl ester resin the most according to claim 1, it is characterised in that include each component of following mass percent:
Low smoke and zero halogen heat-resistant fireproof vinyl ester resin the most according to claim 1 and 2, it is characterised in that: catalyst is a kind of in tetramethyl ammonium chloride, triethanolamine, m-diaminobenzene., N, accelerine.
Low smoke and zero halogen heat-resistant fireproof vinyl ester resin the most according to claim 1 and 2, it is characterised in that: described unsaturated monocarboxylic acid is a kind of in methacrylic acid, acrylic acid, butenoic acid.
Low smoke and zero halogen heat-resistant fireproof vinyl ester resin the most according to claim 1 and 2, it is characterised in that: described polymerization inhibitor is a kind of in hydroquinone, benzoquinone, tert-butyl catechol.
Low smoke and zero halogen heat-resistant fireproof vinyl ester resin the most according to claim 1 and 2, it is characterised in that: described crosslinkable monomers is styrene and/or methyl methacrylate.
7. one kind as arbitrary in claim 1～6 as described in the preparation method of low smoke and zero halogen heat-resistant fireproof vinyl ester resin: be by raw material A, B, C, D, E are put into reactor, at 85～120 DEG C, reaction 2～6 hours, it is then dissolved in F, adding additive flame retardant G after being down to room temperature to stir, airtight preservation prepares.
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| CN104387564B (en) * | 2014-11-04 | 2016-09-14 | 中国林业科学研究院林产化学工业研究所 | The preparation method of flame retardant type Fructus Citri tangerinae quintessence oil base vinyl ester resin monomer |
| WO2016078149A1 (en) * | 2014-11-19 | 2016-05-26 | 俞志红 | Photosensitive phenolic epoxy resin |
| CN104693378A (en) * | 2015-03-24 | 2015-06-10 | 上海米维矿业科技有限公司 | Rapid concretion seriflux injecting material for coal mine laneway water flow sand layer and preparing method thereof |
| CN104910352A (en) * | 2015-05-26 | 2015-09-16 | 常州华科聚合物股份有限公司 | Vinyl ester resin for mold and preparation method thereof |
| CN106188499B (en) * | 2016-07-14 | 2018-05-11 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of flame retardant type castor oil-base vinyl ester resin monomer |
| CN106832797A (en) * | 2016-12-29 | 2017-06-13 | 浙江诺比高分子材料有限公司 | A kind of flame-proof ethylene base resin and its preparation technology |
| CN106832793A (en) * | 2016-12-29 | 2017-06-13 | 浙江诺比高分子材料有限公司 | A kind of optical cable strengthens core vinylite |
| CN107383337A (en) * | 2017-07-31 | 2017-11-24 | 镇江利德尔复合材料有限公司 | A kind of halogen-free flame-retardant vinyl ester resin and preparation method thereof |
| CN107603159B (en) * | 2017-09-18 | 2020-02-04 | 张家港九力新材料科技有限公司 | Flame-retardant compound vinyl alkyd resin and preparation method thereof |
| CN107759749A (en) * | 2017-10-27 | 2018-03-06 | 常州华科聚合物股份有限公司 | Reaction-type flame-retarding vinyl ester resin of synergy and preparation method thereof |
| CN111605221A (en) * | 2020-06-02 | 2020-09-01 | 常州市新创智能科技有限公司 | Preparation method of composite material of flame-retardant fast curing resin by HMP process |
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