CN111499801B - Reactive flame retardant and vinyl SMC resin containing same - Google Patents
Reactive flame retardant and vinyl SMC resin containing same Download PDFInfo
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- CN111499801B CN111499801B CN202010334576.7A CN202010334576A CN111499801B CN 111499801 B CN111499801 B CN 111499801B CN 202010334576 A CN202010334576 A CN 202010334576A CN 111499801 B CN111499801 B CN 111499801B
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- 229920005989 resin Polymers 0.000 title claims abstract description 127
- 239000011347 resin Substances 0.000 title claims abstract description 127
- 239000003063 flame retardant Substances 0.000 title claims abstract description 81
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 64
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 51
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011574 phosphorus Substances 0.000 claims abstract description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 21
- 230000008719 thickening Effects 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000012360 testing method Methods 0.000 claims description 24
- 239000004593 Epoxy Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 230000008859 change Effects 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- 239000002562 thickening agent Substances 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 claims description 6
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 238000006473 carboxylation reaction Methods 0.000 claims description 5
- 150000003972 cyclic carboxylic anhydrides Chemical class 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 238000007142 ring opening reaction Methods 0.000 claims description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 4
- QXONIHMUSQFKJU-UHFFFAOYSA-N 2-(prop-1-enoxymethyl)oxirane Chemical compound CC=COCC1CO1 QXONIHMUSQFKJU-UHFFFAOYSA-N 0.000 claims description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 4
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 claims description 3
- -1 unsaturated cyclic carboxylic acid anhydride Chemical class 0.000 claims description 3
- 230000021523 carboxylation Effects 0.000 claims 1
- 239000003677 Sheet moulding compound Substances 0.000 abstract description 22
- 238000000034 method Methods 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000002131 composite material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 125000002843 carboxylic acid group Chemical group 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000009471 action Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- Macromonomer-Based Addition Polymer (AREA)
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Abstract
The invention discloses a reactive flame retardant and vinyl SMC (sheet molding compound) resin containing the same, belonging to the fields of polymer synthesis and resin preparation. The method comprises the following steps: preparing a polycarboxyl compound containing phosphorus and double bonds; and preparing the flame-retardant vinyl SMC resin. According to the invention, the polycarboxyl compound containing phosphorus and double bonds is prepared and added into the vinyl resin, so that the flame retardant property of a resin cured product can be improved, the thickening reaction of carboxyl and magnesium oxide is utilized to make the vinyl resin completely suitable for the traditional thickening technology, and the problem of vinyl resin thickening troubling the industry is solved. The flame retardant can be connected in a polymer cross-linked network after resin curing through chemical bonds, the addition amount is obviously increased compared with the addition type flame retardant in the prior art, and the flame retardant is beneficial to simultaneously ensuring the flame retardant property and the mechanical property of a resin cured product.
Description
Technical Field
The invention belongs to the field of polymer synthesis and resin preparation, and particularly relates to a reactive flame retardant and vinyl SMC (sheet molding compound) resin containing the same.
Background
SMC is a highly efficient process for the mechanized production of composites, generally prepared from unsaturated polyester resins end-capped with carboxylic acid groups. The principle is that under the action of thickening agent such as magnesium oxide, the mixture of resin, fiber and filler is tackified to a plastic state with certain strength at a proper speed by the action of non-covalent bond between carboxylic acid group and magnesium oxide, and then the plastic is solidified and formed in a die by a die press at high temperature and high pressure. The performance of the vinyl resin is obviously improved compared with that of unsaturated polyester, but the vinyl resin can not be directly manufactured by adopting the method for mould pressing the composite material because the molecular chain does not contain any carboxylic acid group.
On one hand, in order to expand the application field of vinyl resin, the prior art mainly adopts the following means: (1) chemically modifying epoxy vinyl resin, and performing anhydride esterification reaction by using a small amount of hydroxyl on the molecular chain of the epoxy vinyl resin to generate carboxylic acid groups, such as patents CN201310404436.2, CN201611243706.6 and CN201210591993.5 which adopt the means; (2) isocyanate and alcohols are added into resin, and the aim of thickening is achieved by utilizing the reaction of isocyanate groups and hydroxyl groups to realize the rapid increase of molecular weight, such as patents CN201610084522.3 and CN 201811443559.6.
On the other hand, in order to improve the flame retardant property of the flame retardant composite material prepared by the SMC process, the flame retardant property of the composite material is mainly improved by adding the inorganic filler into the resin formula, for example, patents CN201810610118.4, CN201910201735.3, CN201711381754.6, CN201810518963.9 and the like are all means of the same type, and the mechanical property of the composite material is obviously influenced when the addition amount of the inorganic flame retardant filler reaches a certain amount.
Disclosure of Invention
The purpose of the invention is as follows: to solve the problems involved in the background art, there are provided a reactive flame retardant and a vinyl SMC resin comprising the same.
The technical scheme is as follows: the invention provides a thickening reactive flame retardant, which is prepared by the ring-opening reaction of monoalkyl phosphate and a compound with a single epoxy structure and then the carboxylation reaction of the monoalkyl phosphate and an unsaturated cyclic carboxylic anhydride;
the structure is as follows:
The invention also provides a preparation method of the reactive flame retardant capable of thickening, which comprises the following steps: adding 1mol of monoalkyl phosphate into a ceramic reaction kettle, adding 2mol of a compound containing a single epoxy structure, reacting for 0.5h at ambient temperature to complete the ring-opening reaction of the monoalkyl phosphate to epoxy, continuously adding 2mol of unsaturated cyclic carboxylic anhydride, heating to 90-120 ℃, and continuously reacting for 0.5-5 h to complete the carboxylation reaction of hydroxyl, thereby preparing the polycarboxyl compound containing phosphorus and double bonds.
Preferably, the compound with a monoepoxy structure is one of butyl glycidyl ether, phenyl glycidyl ether, epichlorohydrin and propenyl glycidyl ether.
Preferably, the unsaturated cyclic carboxylic acid anhydride is maleic anhydride.
As a preferable embodiment, the structural formula of the polycarboxyl compound containing phosphorus and double bonds is as follows:
The invention also provides flame-retardant vinyl SMC resin, which comprises the following components:
vinyl resin 100 parts by weight
20-80 parts of flame retardant
1-3 parts of curing agent
1.5-3 parts of thickening agent;
after the resin is prepared, continuously testing the viscosity change of the resin, curing the resin in a high-temperature oven at 120-150 ℃ after the viscosity of the resin is not changed, and testing the mechanical property and the flame retardant property of a cured product.
Preferably, the vinyl resin is one of epoxy vinyl resin or polyurethane vinyl resin.
Preferably, the curing agent is one of tert-butyl peroxybenzoate, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide and tert-butyl peroxyacetate.
Preferably, the thickener is one of magnesium oxide, magnesium hydroxide, calcium oxide and calcium hydroxide.
Has the advantages that: the invention relates to a reactive flame retardant and vinyl SMC (sheet molding compound) resin containing the flame retardant. Compared with the prior art, the method has the following advantages: (1) the vinyl resin can simultaneously solve the problems of flame retardance and thickening only by adding one substance of the prepared polycarboxyl compound containing phosphorus and double bonds; (2) the preparation process flow is simple, convenient and mild, complex equipment and harsh reaction conditions are not needed, and the energy consumption is obviously reduced; (3) the flame retardant is reactive, and even if used in large amount, the flame retardant can ensure the flame retardant property of the vinyl resin condensate without reducing the mechanical property of the resin condensate; (3) all raw materials are wide in source and low in price, and the product cost can be effectively reduced while the mechanical property and the flame retardant property are ensured.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without one or more of these specific details. In other instances, well-known features have not been described in order to avoid obscuring the invention.
On one hand, in order to expand the application field of vinyl resin and improve the viscosity of vinyl resin, the prior art mainly adopts the following means: (1) chemically modifying epoxy vinyl resin, and performing anhydride esterification reaction by using a small amount of hydroxyl on the molecular chain of the epoxy vinyl resin to generate carboxylic acid groups; (2) isocyanate and alcohol substances are added into the resin, and the reaction of isocyanate groups and hydroxyl groups is utilized to realize the rapid increase of molecular weight so as to achieve the purpose of thickening.
On the other hand, in order to improve the flame retardant property of the flame retardant composite material prepared by the SMC process, the flame retardant property of the composite material is mainly improved by adding the inorganic filler into the resin formula, but the mechanical property of the composite material is obviously influenced when the addition amount of the inorganic flame retardant filler reaches a certain amount.
The invention mainly prepares a polycarboxyl compound containing phosphorus and double bonds, and adds the polycarboxyl compound into vinyl resin, so that on one hand, the flame retardant property of a resin cured product can be improved, on the other hand, the thickening reaction of carboxyl and magnesium oxide is utilized to ensure that the vinyl resin is completely suitable for the traditional thickening technology, and the problem of vinyl resin thickening puzzling the industry is solved. The specific synthesis process is as follows: adding m-mole phosphoric acid monoalkyl ester into a ceramic reaction kettle, adding 2 m-mole compound containing a single epoxy structure, reacting for 0.5h at ambient temperature to complete the ring-opening reaction of the phosphoric acid monoalkyl ester on epoxy, continuously adding 2 m-mole unsaturated cyclic carboxylic anhydride, heating to 90-120 ℃, and continuously reacting for 0.5-5 h to complete the carboxylation reaction of hydroxyl, thereby preparing the polycarboxyl compound containing phosphorus and double bonds. The compound with the mono-epoxy structure is one of butyl glycidyl ether, phenyl glycidyl ether, epichlorohydrin and propenyl glycidyl ether. The unsaturated cyclic carboxylic acid anhydride is maleic anhydride. The concrete structure is as follows:
Based on the flame retardant, the flame retardant is applied to flame-retardant vinyl SMC resin, and comprises the following components:
vinyl resin 100 parts by weight
20-80 parts of flame retardant
1-3 parts of curing agent
1.5-3 parts of thickening agent;
after the resin is prepared, continuously testing the viscosity change of the resin, curing the resin in a high-temperature oven at 120-150 ℃ after the viscosity of the resin is not changed, and testing the mechanical property and the flame retardant property of a cured product.
The vinyl resin is a linear oligomer containing unsaturated double bonds, and is specifically exemplified by one of epoxy vinyl resin or polyurethane vinyl resin. On one hand, double bonds on long-chain molecules of the vinyl resin and a reactive flame retardant containing double-bond monomer molecules can perform free radical polymerization reaction under the condition of an initiator, so that a more complex three-dimensional network structure is formed; the curing agent is one of tert-butyl peroxybenzoate, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide and tert-butyl peroxyacetate; on the other hand, the thickening reaction of the carboxyl on the reactive flame retardant and the thickening agent is utilized to realize the thickening of the vinyl resin; the thickener is one of magnesium oxide, magnesium hydroxide, calcium oxide and calcium hydroxide. The flame retardant can be connected in a polymer cross-linked three-dimensional network structure after resin curing through chemical bonds, so that the addition amount of the flame retardant is obviously increased compared with that of the traditional additive flame retardant, and the flame retardant is beneficial to simultaneously ensuring the flame retardant property and the mechanical property of a resin cured product.
In the process of further research, the higher the concentration of the curing agent is, the more initial free radicals are generated by the curing agent in unit time, the more the initial free radicals are, the free radical reaction of the vinyl resin and the flame retardant can be accelerated, and the free radical polymerization reaction is an exothermic reaction, so that the temperature of a system is increased, and the reaction rate is further accelerated; however, vinyl resin systems are limited in the double bond content and therefore their reaction rate cannot be increased indefinitely, so that the tendency to reduce the gel time of the unsaturated resin is not apparent when the curing agent content exceeds a certain threshold value. On the other hand, with the increase of the initial content of the curing agent, the viscosity of the vinyl resin is gradually increased, the tensile strength of the finished vinyl resin is also gradually increased, and after the content of the curing agent is more than 3 parts by weight, the curing degree of the unsaturated resin is higher, but the content of the small molecular monomer in the cured cross-linked network structure is lower, so that the finished unsaturated resin shows great brittleness, and the tensile strength of the finished unsaturated resin is greatly reduced. Therefore, the curing agent is preferably in the range of 1-3 parts by weight in consideration of factors such as the curing rate, the economic cost, the mechanical property of the finished resin and the like.
Compared with the prior art, the invention can solve the following problems: (1) the problem of difficult thickening of the vinyl resin is solved by using the traditional technology and raw materials, and the application of the vinyl resin in the SMC technology is realized; (2) different from the prior technical means that only a large amount of inorganic filler can be added, the invention provides a technical approach for simultaneously improving the mechanical properties and the flame retardance of the vinyl resin condensate and the SMC product; (3) the production process of the flame retardant is simple, convenient and mild, the raw materials are wide in source and low in price, no additional equipment is needed for assistance during production, and no byproducts or industrial three wastes are produced.
The invention will now be further described with reference to the following examples, which are intended to be illustrative of the invention and are not to be construed as limiting the invention. The examples, where specific techniques and reaction conditions are not indicated, can be carried out according to the techniques or conditions or product specifications described in the literature in the field. Reagents, instruments or equipment of any manufacturer not indicated are commercially available.
Example 1
10mol of monomethyl phosphate (R is-CH)3) Adding 20mol of butyl glycidyl ether into a ceramic kettle, stirring for 0.5h at ambient temperature, continuously adding 20mol of maleic anhydride, heating to 90 ℃, stirring for 5h,
obtaining a polycarboxyl compound flame retardant (R) containing phosphorus and double bonds1Is composed of) The flame retardant had a molecular weight of 536g/mol and a phosphorus content of 5.78%.
The flame-retardant vinyl SMC resin has the following formula:
epoxy vinyl resin (Shanghai Huachang, MFE-711) 100 parts by weight
20 parts by weight of polycarboxyl compound
1.5 parts by weight of tert-butyl peroxybenzoate
3 parts by weight of magnesium oxide
After the preparation of the resin is finished, continuously testing the viscosity change of the resin, putting the resin into a high-temperature oven at 130 ℃ for curing when the viscosity of the resin is not changed, and testing the mechanical property and the flame retardant property of a cured product.
Example 2
10mol of mono butyl phosphate (R is-C)4H9) Adding 20mol of epichlorohydrin into a ceramic kettle, stirring for 0.5h at ambient temperature, continuously adding 20mol of maleic anhydride, heating to 140 ℃, stirring for 0.5h,
obtaining a polycarboxyl compound flame retardant (R) containing phosphorus and double bonds1Is composed of) The molecular weight of the flame retardant is 530g/mol, and the phosphorus content is 5.85%.
The flame-retardant vinyl SMC resin has the following formula:
polyurethane vinyl resin (Nantong Martaceae, Ureplu-1119): 100 parts by weight
80 parts by weight of polycarboxyl compound
Dicumyl peroxide 3 weight parts
1.5 parts by weight of calcium hydroxide
After the preparation of the resin is finished, continuously testing the viscosity change of the resin, putting the resin into a high-temperature oven at 130 ℃ for curing when the viscosity of the resin is not changed, and testing the mechanical property and the flame retardant property of a cured product.
Example 3
10mol of phosphoric acid mono-octadecyl ester (R is-C)18H37) Adding 20mol of propenyl glycidyl ether into a ceramic kettle, stirring for 0.5h at ambient temperature, continuously adding 20mol of maleic anhydride, heating to 120 ℃, and stirring for 2.5h to obtain the polycarboxyl compound flame retardant (R) containing phosphorus and double bonds1Is composed of) The molecular weight of the flame retardant is 742g/mol, and the phosphorus content is 4.17%.
The flame-retardant vinyl SMC resin has the following formula:
100 parts by weight of a polyurethane vinyl resin (Ureplu-1119, Nantong Martaceae Co., Ltd.)
50 parts by weight of polycarboxyl compound
Di-tert-butyl peroxide 2 parts by weight
2.5 parts by weight of magnesium hydroxide
After the preparation of the resin is finished, continuously testing the viscosity change of the resin, putting the resin into a high-temperature oven at 130 ℃ for curing when the viscosity of the resin is not changed, and testing the mechanical property and the flame retardant property of a cured product.
Example 4
10mol of phosphoric acid monodecadiester (R is-C)12H25) Adding 20mol of phenyl glycidyl ether into a ceramic kettle, stirring for 0.5h at ambient temperature, continuously adding 20mol of maleic anhydride, heating to 130 ℃, and stirring for 1.5h to obtain the polycarboxyl compound flame retardant (R) containing phosphorus and double bonds1Is composed of) The molecular weight of the flame retardant is 730g/mol, and the phosphorus content is 4.25%.
The flame-retardant vinyl SMC resin has the following formula:
epoxy vinyl resin (FX-437, Wenxin, Changzhou) 100 parts by weight
70 parts by weight of polycarboxyl compound
2.5 parts by weight of tert-butyl cumyl peroxide
2 parts by weight of calcium oxide
After the preparation of the resin is finished, continuously testing the viscosity change of the resin, putting the resin into a high-temperature oven at 130 ℃ for curing when the viscosity of the resin is not changed, and testing the mechanical property and the flame retardant property of a cured product.
Example 5
10mol of phosphoric acid monodecadiester (R is-C)12H25) Adding 20mol of phenyl glycidyl ether into a ceramic kettle, stirring for 0.5h at ambient temperature, continuously adding 20mol of maleic anhydride, heating to 130 ℃, and stirring for 1.5h to obtain the polycarboxyl compound flame retardant (R) containing phosphorus and double bonds1Is composed of) The molecular weight of the flame retardant is 730g/mol, and the phosphorus content is 4.25%.
The flame-retardant vinyl SMC resin has the following formula:
epoxy vinyl resin (FX-437, Wenxin, Changzhou) 100 parts by weight
70 parts by weight of polycarboxyl compound
1 part by weight of tert-butyl cumyl peroxide
2 parts by weight of calcium oxide
After the preparation of the resin is finished, continuously testing the viscosity change of the resin, putting the resin into a high-temperature oven at 130 ℃ for curing when the viscosity of the resin is not changed, and testing the mechanical property and the flame retardant property of a cured product.
Example 6
10mol of phosphoric acid monodecadiester (R is-C)12H25) Adding 20mol of phenyl glycidyl ether into a ceramic kettle, stirring for 0.5h at ambient temperature, continuously adding 20mol of maleic anhydride, heating to 130 ℃, and stirring for 1.5h to obtain the polycarboxyl compound flame retardant (R) containing phosphorus and double bonds1Is composed of) The molecular weight of the flame retardant is 730g/mol, and the phosphorus content is 4.25%.
The flame-retardant vinyl SMC resin has the following formula:
epoxy vinyl resin (FX-437, Wenxin, Changzhou) 100 parts by weight
70 parts by weight of polycarboxyl compound
5 parts by weight of tert-butyl cumyl peroxide
2 parts by weight of calcium oxide
After the preparation of the resin is finished, continuously testing the viscosity change of the resin, putting the resin into a high-temperature oven at 130 ℃ for curing when the viscosity of the resin is not changed, and testing the mechanical property and the flame retardant property of a cured product.
Comparative examples 1 to 4
Commercially available flame retardants 1 to 4 were purchased to replace the reactive flame retardants in the formulations of examples 1 to 4, respectively, and the resins of comparative examples 1 to 4 were prepared according to the formulations of examples 1 to 4, and the viscosity of the prepared resins was measured, and after the viscosity of the resins did not change, the resins were put into a high-temperature oven at 130 ℃ to be cured, and the mechanical and flame retardant properties of the cured products were measured.
Example of detection
The resins obtained in the above examples and comparative examples were subjected to mechanical tests and flame retardancy tests, wherein the flame retardancy test standards were as follows: UL94: 2011V 0, V1 and V2.
Examples test data are as follows:
the test data for the comparative examples are as follows:
from the test data in the table above, it can be seen that the viscosity of the resin glue solution can be increased to over 500 ten thousand mpa · s by the polycarboxyl compound of the invention under the action of the thickener, while the comparative example has no such effect, and the viscosity is not substantially changed obviously; in addition, because the polycarboxyl compound can participate in the curing reaction of the vinyl resin, the mechanical property of a resin cured product is not obviously reduced after a large amount of the polycarboxyl compound is added, and the resin cured product has obvious advantages compared with a comparative example. All flame-retardant elements are fixed in the cross-linked network of the cured product by chemical bonds, so the flame-retardant effect is better than that of a comparative example.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
Claims (5)
1. A thickening reactive flame retardant is characterized in that a compound with a mono-epoxy structure reacts with mono-alkyl phosphate through ring opening, and then the compound reacts with unsaturated cyclic carboxylic anhydride through carboxylation to obtain a reactive flame retardant containing multi-carboxyl containing phosphorus and double bonds;
the preparation method of the flame retardant comprises the following steps: adding 1mol of monoalkyl phosphate into a ceramic reaction kettle, adding 2mol of a compound containing a single epoxy structure, reacting for 0.5h at ambient temperature to complete the ring-opening reaction of the monoalkyl phosphate to epoxy, continuously adding 2mol of unsaturated cyclic carboxylic anhydride, heating to 90-120 ℃, and continuously reacting for 0.5-5 h to complete the carboxylation reaction of hydroxyl, thereby preparing a polycarboxyl compound containing phosphorus and double bonds;
the structure is as follows:
the compound with the mono-epoxy structure is one of butyl glycidyl ether, phenyl glycidyl ether, epichlorohydrin and propenyl glycidyl ether;
the unsaturated cyclic carboxylic acid anhydride is maleic anhydride.
2. The flame-retardant vinyl SMC resin is characterized by comprising the following components:
vinyl resin 100 parts by weight
The flame retardant of claim 1 in an amount of 20 to 80 parts by weight
1-3 parts of curing agent
1.5-3 parts of thickening agent;
after the resin is prepared, continuously testing the viscosity change of the resin, curing the resin in a high-temperature oven at 120-150 ℃ after the viscosity of the resin is not changed, and testing the mechanical property and the flame retardant property of a cured product.
3. The flame retardant vinyl SMC resin of claim 2 wherein the vinyl resin is one of an epoxy vinyl resin or a polyurethane vinyl resin.
4. The flame retardant vinyl SMC resin of claim 2 wherein the curing agent includes at least one of tert-butyl peroxybenzoate, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxyacetate.
5. The flame retardant vinyl SMC resin of claim 2 wherein the thickener includes at least one of magnesium oxide, magnesium hydroxide, calcium oxide, and calcium hydroxide.
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CN110684161A (en) * | 2019-11-11 | 2020-01-14 | 中建材料技术研究成都有限公司 | Preparation method of polycarboxylate superplasticizer containing phosphate |
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CN102786717A (en) * | 2012-07-19 | 2012-11-21 | 江汉大学 | Acylamino-containing dialkyl phosphinic acid fire retardant and its preparation method |
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