CN116874994A - High-toughness flame-retardant foamed plastic and preparation method thereof - Google Patents
High-toughness flame-retardant foamed plastic and preparation method thereof Download PDFInfo
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- CN116874994A CN116874994A CN202310929451.2A CN202310929451A CN116874994A CN 116874994 A CN116874994 A CN 116874994A CN 202310929451 A CN202310929451 A CN 202310929451A CN 116874994 A CN116874994 A CN 116874994A
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- talcum powder
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- 229920003023 plastic Polymers 0.000 title claims abstract description 58
- 239000004033 plastic Substances 0.000 title claims abstract description 58
- 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 48
- 239000003063 flame retardant Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- -1 polysiloxane Polymers 0.000 claims abstract description 67
- 239000006260 foam Substances 0.000 claims abstract description 26
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 25
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 24
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 23
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004327 boric acid Substances 0.000 claims abstract description 18
- RVCHQYCXJDVJQF-UHFFFAOYSA-N (3,5-diethylphenyl)methanediamine Chemical compound CCC1=CC(CC)=CC(C(N)N)=C1 RVCHQYCXJDVJQF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004156 Azodicarbonamide Substances 0.000 claims abstract description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 11
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims abstract description 11
- 235000019399 azodicarbonamide Nutrition 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 239000011737 fluorine Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 229920000728 polyester Polymers 0.000 claims abstract description 11
- 229920001225 polyester resin Polymers 0.000 claims abstract description 11
- 239000004645 polyester resin Substances 0.000 claims abstract description 11
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 35
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 27
- 239000000440 bentonite Substances 0.000 claims description 22
- 229910000278 bentonite Inorganic materials 0.000 claims description 22
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 22
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 22
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 19
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 17
- XKUYOJZZLGFZTC-UHFFFAOYSA-K lanthanum(iii) bromide Chemical compound Br[La](Br)Br XKUYOJZZLGFZTC-UHFFFAOYSA-K 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 239000004698 Polyethylene Substances 0.000 claims description 12
- 229920000573 polyethylene Polymers 0.000 claims description 12
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 7
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical group CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 235000012222 talc Nutrition 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 229920000587 hyperbranched polymer Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
- C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
- C08J9/008—Nanoparticles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/02—Copolymers with acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
Abstract
The invention relates to the field of flame-retardant foam plastics, in particular to a high-toughness flame-retardant foam plastic and a preparation method thereof. The plastic is prepared from the following components: polyester resin, liquid nitrile rubber, hydroxyl-terminated fluorine-containing polyester polysiloxane, azodicarbonamide, triethylenediamine, 3, 5-diethyl toluenediamine, boric acid compound, talcum powder modified flame retardant and rare earth reinforcing agent. The plastic provided by the invention has the advantages that the crystal density is high, oxygen molecules are difficult to penetrate into the plastic at high temperature, the strength of the plastic can be enhanced, the flame retardance and corrosion resistance of the plastic can be improved, the application range is wide, and the economic value is high.
Description
Technical Field
The invention relates to the field of flame-retardant foam plastics, in particular to a high-toughness flame-retardant foam plastic and a preparation method thereof.
Background
Flame retardant or flame retardant plastic. The flame retardance is commonly measured by oxygen index: plastics with oxygen index below 22 are easy to burn and have no combustibility, the oxygen index between 22 and 27 are flame-retardant and have self-extinguishing property, and the oxygen index is higher than 27 and is high in flame retardance. The Oxygen Index (OI) is the minimum oxygen concentration required to maintain stable combustion of a sample in a mixed oxygen and nitrogen stream during a flammability test. The oxygen index of the flame retardant plastic should be above 22. The flame retardant is added into plastics, namely the added flame retardant plastics, and the other type is that the polymer itself contains a flame retardant structure and can be used for flame retardance without adding the flame retardant, namely the structural flame retardant plastics. The flame retardant is inorganic and organic, and the inorganic flame retardant comprises antimonous oxide, hydrated alumina, zinc borate and the like; the organic flame retardant is mainly halogenated hydrocarbon, such as chlorinated paraffin, chlorinated polyethylene, hexabromobenzene and the like. The burning of halogenated hydrocarbon produces hydrogen chloride, hydrogen bromide and other powerful stimulation, toxic and choking gas, so that it is important to research non-toxic or low-toxic flame retardant plastic with non-halogen structure. The flame retardant plastic has a great variety and wide application. Such as passenger plane cabin, plastic structure and decoration material in high-grade hotel and market, and shell and parts of electronic, household appliances, instruments and meters, etc. are made of flame-retardant plastic in large quantity, so as to raise use safety and avoid great loss caused by fire.
In the prior art, a lot of researches are carried out on flame retardance of plastics, such as whisker reinforced and toughened halogen-free flame retardant phenolic foam plastic with a patent number of CN201710261836.0 and a preparation method thereof, wherein the plastic is prepared from expandable phenolic resin, a toughening agent, a surfactant, a foaming agent, a curing agent, a flame retardant and a whisker reinforcing agent, and the strength and toughness of the phenolic foam material are improved by using a small amount of whisker; in another example, the patent number is CN201810830867.8, ABS resin and a toughening agent are mixed uniformly, then a metal modified hyperbranched polymer is added, and the mixture is mixed uniformly again and then melted and granulated to prepare the flame-retardant engineering plastic, wherein the metal modified hyperbranched polymer is a network polymer formed by crosslinking a hyperbranched polymer with carboxyl groups at end groups and metal ions, but the molecular network has poor restriction on crystals and insufficient toughness, and is difficult to adapt to wide-range use.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a high-toughness flame-retardant foamed plastic and a preparation method thereof, which are used for enhancing the stability of the plastic at high temperature and enhancing the flame retardance of the plastic, wherein the plastic is prepared from the following components in parts by weight: 120-150 parts of polyester resin, 3-8 parts of liquid nitrile rubber, 5-10 parts of hydroxyl-terminated fluorine-containing polyester polysiloxane, 10-15 parts of azodicarbonamide, 5-10 parts of triethylenediamine, 3-8 parts of 3, 5-diethyl toluenediamine, 1-3 parts of boric acid compound, 3-5 parts of talcum powder modified flame retardant and 1-3 parts of rare earth reinforcing agent.
Further, the talcum powder modified flame retardant is prepared from 11-15 parts of nano talcum powder, 2-4 parts of silane coupling agent, 3-5 parts of acid and 0.1-0.5 part of calcium sulfate whisker.
Further, the boric acid compound is formed by mixing calcium borate and zinc borate in a mass ratio of 1:3-4.
Further, the rare earth reinforcing agent is formed by mixing lanthanum bromide, cerium chloride, yttrium oxide, bentonite and polyethylene in a mass ratio of 1:2-3:2-5:8-15:20-23.
Further, the silane coupling agent is isobutyl triethoxysilane.
Further, the acid is 15-18% phosphoric acid by mass fraction.
The preparation method of the high-toughness flame-retardant foam plastic disclosed by the invention comprises the following steps of:
(1) Preparation of talcum powder modified flame retardant
Heating nano talcum powder under vacuum for 30-50min, cooling to room temperature, mixing nano talcum powder with 15-18 parts of clear water, stirring at 330-520r/min for 30-50min, heating to 35-40 ℃, adding acid, stirring at 500-700r/min for 70-80min, adding silane coupling agent, standing for 3-5min, cooling to minus 30-50 ℃ and freezing for 3-5h; heating to room temperature by microwave, adding calcium sulfate whisker, stirring at a rotating speed of 800-1000r/min for 2-3h, and drying under reduced pressure to obtain the talcum powder modified flame retardant;
(2) Preparation of rare earth reinforcing agent
Uniformly mixing lanthanum bromide and cerium chloride, adding deionized water with the mass 70-75 times of that of the lanthanum bromide and cerium chloride, stirring for 10-15min, adding bentonite for 5 times in equal amount, stirring for 5-8min at 500-600r/min after each bentonite addition, drying the mixture at 100-200 ℃ and 0.1-0.3 standard atmospheric pressure for 50-80min after the addition, mixing the dried product with polyethylene and yttrium oxide, heating to a molten state, stirring uniformly, cooling and drying, and processing into superfine powder for later use;
(3) Rubber miscibility
Uniformly mixing liquid nitrile rubber with a rare earth reinforcing agent, heating to 50-60 ℃ and stirring for 10-15min to obtain a mixture A for later use;
(4) Premixing
Uniformly mixing polyester resin, hydroxyl-terminated fluorine-containing polyester polysiloxane, boric acid compound and talcum powder modified flame retardant to obtain a mixture B for standby;
(5) Preparation of high-toughness flame-retardant foam plastic
Pouring the mixture A and the mixture B into a stirrer, adding azodicarbonamide, triethylenediamine and 3, 5-diethyl toluenediamine, stirring uniformly, pouring into a mould at 60-65 ℃ for standing for 3-5h, and heating under vacuum to the temperature of 100-120 ℃ for 5-8 min.
The invention has the beneficial effects that:
according to the invention, through utilizing the characteristic of a talcum powder multilayer structure, the phosphate content in the talcum powder is increased through phosphoric acid adsorption reaction, so that the surface and the interlayer of the talcum powder have more phosphate crystal protrusions, the roughness of the talcum powder is improved, then the silane coupling agent solution and the talcum powder are mixed, the solidified volume expansion of water molecules is utilized to prop up the interlayer distance of the talcum powder through low-temperature freezing, then the silane coupling agent is promoted to be inserted between the talcum powder layers through the microwave effect, so that the talcum powder has more molecular chain extension, the combination of the talcum powder to the silane coupling agent is enhanced, the compatibility of the talcum powder and plastics is improved, the cementation of the talcum powder and other components in the plastics is enhanced, the crystal density of the talcum powder is improved, so that oxygen molecules are difficult to permeate into the inside of the plastics at high temperature, and the heavy components in the plastics are increased through the talcum powder, the strength of the plastics can be enhanced, and the flame retardance of the plastics can be improved.
The invention utilizes the porous strong adsorptivity of bentonite to absorb lanthanum bromide and cerium chloride, so that the molecular space of bentonite is properly filled, and at the same time, the adsorptivity of bentonite is not obviously reduced, and utilizes the adsorption of bentonite to fully mix lanthanum bromide and cerium chloride, and then yttrium oxide and polyethylene are added, so that the whole rare earth reinforcer uses bentonite as the center, contains rare earth atoms with strong compound bond adsorption and polyethylene molecular chains with high-temperature lubrication effect, so that the molecular network in plastics is densely crosslinked, the molecular complexity is increased, the boric acid compound has strong coating capability, the flame retardance and corrosion resistance of plastics are better improved, and the strength of plastics is increased.
The invention uses calcium borate and zinc borate, so that the plastic has better thawing effect at high temperature, the plastic can soften the sealed combustion surface at high temperature, so that the combustion can not continue, and meanwhile, the plastic is coordinated and connected with each other by matching with rare earth and talcum powder, so that the effect of oxygen molecules is reduced, and the flame retardant effect of the material is obviously enhanced.
Description of the embodiments
Examples
A high-toughness flame-retardant foam plastic is prepared from the following components in parts by weight: 120 parts of polyester resin, 3 parts of liquid nitrile rubber, 5 parts of hydroxyl-terminated fluorine-containing polyester polysiloxane, 10 parts of azodicarbonamide, 5 parts of triethylenediamine, 3 parts of 3, 5-diethyl toluenediamine, 1 part of boric acid compound, 3 parts of talcum powder modified flame retardant and 1 part of rare earth reinforcing agent; the talcum powder modified flame retardant is prepared from 11 parts of nano talcum powder, 2 parts of silane coupling agent, 3 parts of acid and 0.1 part of calcium sulfate whisker; the silane coupling agent is isobutyl triethoxy silicon; the acid is 15% phosphoric acid by mass fraction; the boric acid compound is formed by mixing calcium borate and zinc borate in a mass ratio of 1:3; the rare earth reinforcing agent is formed by mixing lanthanum bromide, cerium chloride, yttrium oxide, bentonite and polyethylene in a mass ratio of 1:2:2:8:20.
The preparation method of the high-toughness flame-retardant foam plastic disclosed by the embodiment is as follows:
(1) Preparation of talcum powder modified flame retardant
Heating nano talcum powder under vacuum for 30min, cooling to room temperature, mixing the nano talcum powder with 15 parts of clear water by mass, stirring at a rotation speed of 330r/min for 30min, heating to 35 ℃, adding acid, stirring at a rotation speed of 500r/min for 70min, adding a silane coupling agent, standing for 3min, and cooling to minus 30 ℃ for 3h; heating to room temperature by using microwaves, adding calcium sulfate whiskers, stirring for 2 hours at a rotating speed of 800r/min, and drying under reduced pressure to obtain the talcum powder modified flame retardant;
(2) Preparation of rare earth reinforcing agent
Uniformly mixing lanthanum bromide and cerium chloride, adding deionized water with the mass 70 times of the lanthanum bromide and cerium chloride, stirring for 10min, adding bentonite in 5 times of equal amount, stirring for 5min at 500r/min after each bentonite addition, drying the mixture at 100 ℃ under 0.1 standard atmospheric pressure for 50min after the bentonite addition, mixing the dried product with polyethylene and yttrium oxide, heating to a molten state, uniformly stirring, cooling, drying, and processing into superfine powder for later use;
(3) Rubber miscibility
Uniformly mixing liquid nitrile rubber with a rare earth reinforcing agent, heating to 50 ℃, and stirring for 10min to obtain a mixture A for later use;
(4) Premixing
Uniformly mixing polyester resin, hydroxyl-terminated fluorine-containing polyester polysiloxane, boric acid compound and talcum powder modified flame retardant to obtain a mixture B for standby;
(5) Preparation of high-toughness flame-retardant foam plastic
Pouring the mixture A and the mixture B into a stirrer, adding azodicarbonamide, triethylenediamine and 3, 5-diethyl toluenediamine, stirring uniformly, pouring into a mould at 60 ℃ for standing for 3h, and heating to the temperature of 100 ℃ under vacuum for 5 min.
Examples
A high-toughness flame-retardant foam plastic is prepared from the following components in parts by weight: 150 parts of polyester resin, 8 parts of liquid nitrile rubber, 10 parts of hydroxyl-terminated fluorine-containing polyester polysiloxane, 15 parts of azodicarbonamide, 10 parts of triethylenediamine, 8 parts of 3, 5-diethyl toluenediamine, 3 parts of boric acid compound, 5 parts of talcum powder modified flame retardant and 3 parts of rare earth reinforcing agent; the talcum powder modified flame retardant is prepared from 15 parts of nano talcum powder, 4 parts of silane coupling agent, 5 parts of acid and 0.5 part of calcium sulfate whisker; the silane coupling agent is isobutyl triethoxy silicon; the acid is phosphoric acid with the mass fraction of 18%; the boric acid compound is formed by mixing calcium borate and zinc borate with the mass ratio of 1:4; the rare earth reinforcing agent is prepared by mixing lanthanum bromide, cerium chloride, yttrium oxide, bentonite and polyethylene in a mass ratio of 1:3:5:15:23.
The preparation method of the high-toughness flame-retardant foam plastic disclosed by the embodiment is as follows:
(1) Preparation of talcum powder modified flame retardant
Heating nano talcum powder under vacuum for 50min, cooling to room temperature, mixing the nano talcum powder with 18 parts of clear water, stirring at 520r/min for 50min, heating to 40 ℃, adding acid, stirring at 700r/min for 80min, adding silane coupling agent, standing for 5min, and cooling to minus 50 ℃ for 5h; heating to room temperature by using microwaves, adding calcium sulfate whiskers, stirring for 3 hours at a rotating speed of 1000r/min, and drying under reduced pressure to obtain the talcum powder modified flame retardant;
(2) Preparation of rare earth reinforcing agent
Uniformly mixing lanthanum bromide and cerium chloride, adding deionized water with the mass being 5 times of that of the lanthanum bromide and cerium chloride, stirring for 15min, adding bentonite in 5 times of equal amount, stirring for 8min at 600r/min after each bentonite addition, drying the mixture at 200 ℃ and 0.3 standard atmospheric pressure for 80min after the addition, mixing the dried product with polyethylene and yttrium oxide, heating to a molten state, stirring uniformly, cooling and drying, and processing into superfine powder for later use;
(3) Rubber mixing, namely uniformly mixing liquid nitrile rubber with a rare earth reinforcing agent, heating to 60 ℃, and stirring for 15min to obtain a mixture A for later use;
(4) Premixing
Uniformly mixing polyester resin, hydroxyl-terminated fluorine-containing polyester polysiloxane, boric acid compound and talcum powder modified flame retardant to obtain a mixture B for standby;
(5) Preparation of high-toughness flame-retardant foam plastic
Pouring the mixture A and the mixture B into a stirrer, adding azodicarbonamide, triethylenediamine and 3, 5-diethyl toluenediamine, stirring uniformly, pouring into a mold at 65 ℃ for standing for 5 hours, heating to 100-120 ℃ under vacuum, and preserving the temperature for 5-8 min.
Examples
A high-toughness flame-retardant foam plastic is prepared from the following components in parts by weight: 143 parts of polyester resin, 5 parts of liquid nitrile rubber, 6 parts of hydroxyl-terminated fluorine-containing polyester polysiloxane, 14 parts of azodicarbonamide, 10 parts of triethylenediamine, 3 parts of 3, 5-diethyl toluenediamine, 3 parts of boric acid compound, 3 parts of talcum powder modified flame retardant and 1 part of rare earth reinforcing agent; the talcum powder modified flame retardant is prepared from 15 parts of nano talcum powder, 2 parts of silane coupling agent, 5 parts of acid and 0.1 part of calcium sulfate whisker; the silane coupling agent is isobutyl triethoxy silicon; the acid is phosphoric acid with the mass fraction of 18%; the boric acid compound is formed by mixing calcium borate and zinc borate in a mass ratio of 1:3; the rare earth reinforcing agent is formed by mixing lanthanum bromide, cerium chloride, yttrium oxide, bentonite and polyethylene in a mass ratio of 1:3:2:15:20.
The preparation method of the high-toughness flame-retardant foam plastic disclosed by the embodiment is as follows:
(1) Preparation of talcum powder modified flame retardant
Heating nano talcum powder under vacuum for 50min, cooling to room temperature, mixing the nano talcum powder with 15 parts of clear water by mass, stirring at 520r/min for 30min, heating to 40 ℃, adding acid, stirring at 500r/min for 70min, adding silane coupling agent, standing for 5min, and cooling to minus 50 ℃ for 3h; heating to room temperature by using microwaves, adding calcium sulfate whiskers, stirring for 2 hours at a rotating speed of 1000r/min, and drying under reduced pressure to obtain the talcum powder modified flame retardant;
(2) Preparation of rare earth reinforcing agent
Uniformly mixing lanthanum bromide and cerium chloride, adding deionized water with the mass being 75 times of that of the lanthanum bromide and cerium chloride, stirring for 10min, adding bentonite in 5 times of equal amount, stirring for 5min at 600r/min after each bentonite addition, drying the mixture at 200 ℃ and 0.1 standard atmospheric pressure for 80min after the bentonite addition, mixing the dried product with polyethylene and yttrium oxide, heating to a molten state, stirring uniformly, cooling and drying, and processing into superfine powder for later use;
(3) Rubber miscibility
Uniformly mixing liquid nitrile rubber with a rare earth reinforcing agent, and stirring for 10min at a temperature of 60 ℃ to obtain a mixture A for later use;
(4) Premixing
Uniformly mixing polyester resin, hydroxyl-terminated fluorine-containing polyester polysiloxane, boric acid compound and talcum powder modified flame retardant to obtain a mixture B for standby;
(5) Preparation of high-toughness flame-retardant foam plastic
Pouring the mixture A and the mixture B into a stirrer, adding azodicarbonamide, triethylenediamine and 3, 5-diethyl toluenediamine, stirring uniformly, pouring into a mold at 65 ℃ for standing for 3 hours, and heating to 120 ℃ under vacuum and preserving heat for 5 minutes.
To verify the effect of the present invention, the following comparative examples were set up:
| comparative example 1 | The difference from example 1 is that boric acid compound was not used in the raw materials for production; |
| comparative example 2 | The difference from example 1 is that no talc modified flame retardant was used in the raw materials for the manufacture; |
| comparative example 3 | The difference from example 1 is that no rare earth reinforcing agent is used in the raw materials for production; |
| comparative example 4 | The difference from example 1 is that phosphoric acid is not used in the preparation of the talc modified flame retardant; |
| comparative example 5 | The difference from example 1 is that no silane coupling agent is used in the preparation of the talc modified flame retardant; |
| comparative example 6 | The difference from example 1 is that no calcium sulfate whisker was used in the preparation of the talc modified flame retardant. |
Experimental example
Foam was prepared according to examples 1-3 and comparative examples 1-6, the apparent density was measured according to GB/T6343-2009 standard, the compressive strength was measured according to GB/T8813-2008 standard, the flame retardancy of the plastic was measured according to DIN 4102 standard, and the corrosion resistance was measured by placing the plastic in 5% sodium hydroxide solution.
As can be seen from the table, the apparent density of the foams using the process of the present invention exceeds 35.13kg/m 3 The compression strength is more than 0.29MPa, the flame retardant is A grade, and the 5% sodium hydroxide corrosion resistance is more than 600 hours, so that the effect is remarkable.
Claims (7)
1. The high-toughness flame-retardant foam plastic is characterized by being prepared from the following components in parts by weight: 120-150 parts of polyester resin, 3-8 parts of liquid nitrile rubber, 5-10 parts of hydroxyl-terminated fluorine-containing polyester polysiloxane, 10-15 parts of azodicarbonamide, 5-10 parts of triethylenediamine, 3-8 parts of 3, 5-diethyl toluenediamine, 1-3 parts of boric acid compound, 3-5 parts of talcum powder modified flame retardant and 1-3 parts of rare earth reinforcing agent.
2. The high-toughness flame-retardant foam plastic according to claim 1, wherein the talcum powder modified flame retardant is prepared from 11-15 parts of nano talcum powder, 2-4 parts of silane coupling agent, 3-5 parts of acid and 0.1-0.5 part of calcium sulfate whisker.
3. The high-toughness flame-retardant foam according to claim 1, wherein the boric acid compound is formed by mixing calcium borate and zinc borate in a mass ratio of 1:3-4.
4. The high-toughness flame-retardant foam plastic according to claim 1, wherein the rare earth reinforcing agent is prepared by mixing lanthanum bromide, cerium chloride, yttrium oxide, bentonite and polyethylene in a mass ratio of 1:2-3:2-5:8-15:20-23.
5. The high-toughness flame-retardant foam according to claim 2, wherein the silane coupling agent is isobutyl triethoxysilane.
6. The high-toughness flame-retardant foam according to claim 2, wherein the acid is 15 to 18% by mass of phosphoric acid.
7. The high-toughness flame-retardant foam plastic according to claim 1, wherein the preparation method comprises the following steps:
(1) Preparation of talcum powder modified flame retardant
Heating nano talcum powder under vacuum for 30-50min, cooling to room temperature, mixing nano talcum powder with 15-18 parts of clear water, stirring at 330-520r/min for 30-50min, heating to 35-40 ℃, adding acid, stirring at 500-700r/min for 70-80min, adding silane coupling agent, standing for 3-5min, cooling to minus 30-50 ℃ and freezing for 3-5h; heating to room temperature by microwave, adding calcium sulfate whisker, stirring at a rotating speed of 800-1000r/min for 2-3h, and drying under reduced pressure to obtain the talcum powder modified flame retardant;
(2) Preparation of rare earth reinforcing agent
Uniformly mixing lanthanum bromide and cerium chloride, adding deionized water with the mass 70-75 times of that of the lanthanum bromide and cerium chloride, stirring for 10-15min, adding bentonite for 5 times in equal amount, stirring for 5-8min at 500-600r/min after each bentonite addition, drying the mixture at 100-200 ℃ and 0.1-0.3 standard atmospheric pressure for 50-80min after the addition, mixing the dried product with polyethylene and yttrium oxide, heating to a molten state, stirring uniformly, cooling and drying, and processing into superfine powder for later use;
(3) Rubber miscibility
Uniformly mixing liquid nitrile rubber with a rare earth reinforcing agent, heating to 50-60 ℃ and stirring for 10-15min to obtain a mixture A for later use;
(4) Premixing
Uniformly mixing polyester resin, hydroxyl-terminated fluorine-containing polyester polysiloxane, boric acid compound and talcum powder modified flame retardant to obtain a mixture B for standby;
(5) Preparation of high-toughness flame-retardant foam plastic
Pouring the mixture A and the mixture B into a stirrer, adding azodicarbonamide, triethylenediamine and 3, 5-diethyl toluenediamine, stirring uniformly, pouring into a mould at 60-65 ℃ for standing for 3-5h, and heating under vacuum to the temperature of 100-120 ℃ for 5-8 min.
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