CN113861599A - Silica gel-like thermoplastic resin and preparation method thereof - Google Patents
Silica gel-like thermoplastic resin and preparation method thereof Download PDFInfo
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- CN113861599A CN113861599A CN202111251167.1A CN202111251167A CN113861599A CN 113861599 A CN113861599 A CN 113861599A CN 202111251167 A CN202111251167 A CN 202111251167A CN 113861599 A CN113861599 A CN 113861599A
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- thermoplastic resin
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- polyvinyl chloride
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 32
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 67
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 67
- 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 claims abstract description 15
- 239000003063 flame retardant Substances 0.000 claims abstract description 15
- 239000003607 modifier Substances 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 239000004014 plasticizer Substances 0.000 claims abstract description 10
- 239000000945 filler Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000005662 Paraffin oil Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 67
- 238000005303 weighing Methods 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 23
- 229920002545 silicone oil Polymers 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 16
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 16
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 238000007873 sieving Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 9
- 235000013539 calcium stearate Nutrition 0.000 claims description 9
- 239000008116 calcium stearate Substances 0.000 claims description 9
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 9
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 9
- 238000005086 pumping Methods 0.000 claims description 9
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 8
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 8
- 239000012188 paraffin wax Substances 0.000 claims description 8
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 7
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 claims description 7
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 229940075507 glyceryl monostearate Drugs 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 7
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical group O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001746 injection moulding Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 229910021485 fumed silica Inorganic materials 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 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 3
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000005660 chlorination reaction Methods 0.000 description 10
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- -1 polyethylene Polymers 0.000 description 7
- 230000002195 synergetic effect Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/22—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L27/24—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment halogenated
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
- C08F8/22—Halogenation by reaction with free halogens
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application relates to the technical field of thermoplastic resin, in particular to silica gel-like thermoplastic resin and a preparation method thereof, wherein the silica gel-like thermoplastic resin is prepared from the following raw materials in parts by weight: 80-100 parts of modified polyvinyl chloride, 5-30 parts of organic silicon modifier, 3-8 parts of paraffin oil, 5-10 parts of plasticizer, 4-7 parts of flame retardant and 2-5 parts of filler; the silica gel-like thermoplastic resin has higher flame retardance, flexibility, high temperature resistance and the like by adding the modified polyvinyl chloride, and the flame retardance, the flexibility and the high temperature resistance of the silica gel-like thermoplastic resin are further improved by grafting modification through the organic silicon modifier.
Description
Technical Field
The application relates to the technical field of thermoplastic resin, in particular to silica gel-like thermoplastic resin and a preparation method thereof.
Background
The thermoplastic resin has the properties of softening by heating and hardening by cooling, does not react chemically, and can maintain the properties no matter how many times the heating and cooling are repeated, so the thermoplastic resin is widely applied to the fields of coatings, resin toys, wires, cables and the like.
Typical thermoplastic resins include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyamide, polyoxymethylene, polycarbonate, polyphenylene oxide, polysulfone, rubber, and SBS, and generally have poor rigidity, low melting point, and poor heat resistance, and are easily combustible.
Disclosure of Invention
In order to improve the flame retardance of the thermoplastic resin, the application provides the silica gel-like thermoplastic resin and a preparation method thereof.
The application provides an imitation silica gel thermoplastic resin and a preparation method thereof, and the following technical scheme is adopted:
in a first aspect, the silica gel-like thermoplastic resin is prepared from the following raw materials in parts by weight:
modified polyvinyl chloride: 80 to 100 portions of
Silicone modifier: 5-30 parts of
Paraffin oil: 3-8 parts of
Plasticizer: 5-10 parts of
Flame retardant: 4 to 7 portions of
Filling agent: 2-5 parts.
By adopting the technical scheme, the adopted raw materials and the weight parts of the raw materials are in the range of the better proportion and the weight parts in the application; the application adopts the polyethylene modified by the modified polyvinyl chloride through chlorination, the softening temperature of the polyvinyl chloride is generally about 75 ℃, the softening temperature of the polyvinyl chloride modified through chlorination can generally reach about 120 ℃ or even higher, and the modified polyvinyl chloride modified through chlorination has better heat resistance and oxidation resistance compared with the polyvinyl chloride.
The content of chlorine in molecules of the modified polyvinyl chloride obtained by chlorination modification is increased, the polarity of molecular chains of the modified polyvinyl chloride is enhanced, the acting force between molecules is increased, the modified polyvinyl chloride is easier to process or mix with other materials for reaction, and the organic silicon modifier has good heat resistance and flame retardance, and the modified polyvinyl chloride is further modified by organic silicon, so that the heat resistance and the flame retardance of the obtained silica-like thermoplastic resin are improved; the plasticizer improves the plasticity of the silica gel-like thermoplastic resin and is convenient to process; by adding the flame retardant, the silicone-modified thermoplastic resin has a synergistic effect with organic silicon, and can improve the flame retardance of the silica gel-like thermoplastic resin.
The paraffin oil and the plasticizer are added to have a synergistic effect, so that a lubricating effect can be achieved, and the processing of the silica gel-like thermoplastic tree is facilitated; the filler improves the mechanical strength of the silica gel-like thermoplastic resin, so that the prepared silica gel-like thermoplastic resin obtains better flame retardance, high temperature resistance and flexibility through the combination of the substances.
Preferably, the preparation of the modified polyvinyl chloride comprises the following steps:
step 1: weighing 80-100 parts by weight of polyvinyl chloride and 150-200 parts by weight of water, and uniformly mixing to obtain a mixture I;
step 2: weighing 3-5 parts by weight of lauroyl peroxide, 1-2 parts by weight of glyceryl monostearate and 1-3 parts by weight of dimethyltin dichloride, adding into the mixture I obtained in the step 1, uniformly mixing, and vacuumizing to obtain a mixture II;
and step 3: introducing chlorine into the mixture II obtained in the step 2, pressurizing, heating to 50-60 ℃, and reacting for 2-3h to obtain a mixture III;
and 4, step 4: and (3) irradiating the mixture III obtained in the step (3) by using ultraviolet, heating to 70-80 ℃, reacting for 3-5h, cooling, adding a sodium hydroxide solution with the mass fraction of 5-8% for neutralization, washing with water, drying, grinding, and sieving by using a sieve of 100 meshes and 150 meshes to obtain the modified polyvinyl chloride.
By adopting the technical scheme, the lauroyl peroxide and the glyceryl monostearate are added to have a synergistic effect and can be used as an initiator to promote the chlorination reaction of polyethylene, and the dimethyl tin dichloride is added to promote the reaction and improve the stability of the reaction; heating in sections to promote reaction, and simultaneously, irradiating by an ultraviolet lamp to further promote chlorination reaction of polyvinyl chloride to enable the chlorine content of the polyvinyl chloride to reach 64.5-70.2%, so as to prepare the modified polyethylene.
Preferably, the preparation of the polyvinyl chloride comprises the following steps:
s1: weighing 2-5 parts by weight of hydroxymethyl cellulose and 0.5-1 part by weight of calcium stearate, dissolving in 150 parts by weight of water, and uniformly stirring to obtain a mixture A for later use;
s2: weighing 3-5 parts by weight of diisopropyl peroxydicarbonate and 1-2 parts by weight of azobisisoheptonitrile, adding into the mixture A obtained in S1, stirring uniformly, and pumping air to obtain a mixture B;
s3: weighing 40-60 parts by weight of chloroethylene, adding the chloroethylene into the mixture B obtained in the step S2, uniformly stirring, heating to 45-55 ℃, and reacting for 3-5 hours to obtain a mixed solution C;
s4: weighing 1-2 parts by weight of sodium persulfate and 50-60 parts by weight of chloroethylene, heating to 60-75 ℃, reacting for 2-3h, cooling to room temperature, adding 70-80% by mass of ethanol solution for cleaning, dehydrating, drying, grinding, and sieving by a sieve of 100 meshes and 200 meshes to obtain the polyvinyl chloride.
By adopting the technical scheme, the hydroxymethyl cellulose and the calcium stearate are added, the synergistic effect is achieved, the dispersion of the monomers is improved as a suspension stabilizer, the vinyl chloride monomers are added step by step, the polymerization reaction is more sufficient, the polymerization degree of the obtained polyvinyl chloride is larger, the purity is higher, the purity of the modified polyvinyl chloride prepared from the polyvinyl chloride is improved, more modified polyvinyl chloride reacts with the organic silicon modifier, and the heat resistance, the flame retardance and the flexibility of the silica gel-like thermoplastic resin are improved.
Preferably, the plasticizer is one or more of dioctyl phthalate, dibutyl phthalate and chlorinated paraffin.
By adopting the technical scheme, when the dioctyl phthalate, the dibutyl phthalate and the chlorinated paraffin are mixed, the weight ratio of the dioctyl phthalate, the dibutyl phthalate and the chlorinated paraffin is 1:1-3: 2-6; ratios within this range are preferred plasticizer mixture ratios herein; the dioctyl phthalate and the dibutyl phthalate have good mixing performance, high plasticizing efficiency and good heat resistance and weather resistance, and the chlorinated paraffin has the advantages of low volatility, flame retardance, good electrical insulation, low price and the like, and can be used for enhancing the plasticity and the flame retardance of the silica gel-like thermoplastic resin under the synergistic action with the dioctyl phthalate and the dibutyl phthalate.
Preferably, the organic silicon modifier is formed by mixing dimethyl silicone oil, phenyl silicone oil and hydroxyl silicone oil.
By adopting the technical scheme, the dimethyl silicone oil has small surface tension and has the characteristics of corrosion resistance, heat resistance and no toxicity; the phenyl silicone oil has good oxidation stability, heat resistance, flame resistance, ultraviolet resistance and chemical resistance; the hydroxyl silicone oil can be used as a structure control agent and a high temperature resistant agent, and the flame retardance, the flexibility and the high temperature resistance of the silica gel-like thermoplastic resin can be improved through the combination of the three types of organic silicon.
Preferably, the weight ratio of the dimethyl silicone oil to the phenyl silicone oil to the hydroxyl silicone oil is 1: 2-5: 3-8, wherein the weight part is the preferable weight part range ratio in the application, and the flame retardance, the flexibility and the high temperature resistance of the silica gel-like thermoplastic resin can be improved.
Preferably, the flame retardant is antimony trioxide and/or zinc borate, has a synergistic effect, can improve the flame retardant property, reduces the generation of smoke during combustion, and improves the flame retardant property of the silica gel-like thermoplastic resin.
Preferably, the filler is one or a combination of more of fumed silica, kaolin and nano silicon dioxide, and has a reinforcing effect, so that the mechanical property of the silica gel-like thermoplastic resin is improved, and the cost can be reduced.
Preferably, the kaolin, the nano-silica and the fumed silica are in a weight ratio of 1:1-2:1-3, and the weight ratio in the range is a preferable weight ratio in the application, so that the mechanical property of the silica gel-like thermoplastic resin can be enhanced.
In a second aspect, the present application provides a method for preparing a silica gel-like thermoplastic resin, comprising the following steps:
step A: weighing 80-100 parts by weight of modified polyvinyl chloride and 5-10 parts by weight of plasticizer, and uniformly mixing to obtain a mixture 1;
step B: weighing 5-30 parts by weight of organic silicon modifier, 3-8 parts by weight of paraffin oil, 4-7 parts by weight of flame retardant and 2-5 parts by weight of filler, adding the mixture into the mixture 1 obtained in the step 2, uniformly stirring, heating to 155-165 ℃, mixing for 5-15 minutes, and performing injection molding through an injection molding machine at 185-195 ℃ to obtain the silica gel-like thermoplastic resin.
By adopting the technical scheme, the operation is simple, the processing time is short, the production efficiency is high, the materials are uniformly mixed and dispersed, and the prepared silica gel-like thermoplastic resin has excellent flame retardance, flexibility and high temperature resistance.
In summary, the present application has the following beneficial effects:
1. according to the application, modified polyvinyl chloride is adopted to chloridize the modified polyethylene, so that the polarity of the molecular chain of the obtained modified polyvinyl chloride is enhanced, the intermolecular acting force is improved, the modified polyvinyl chloride is easier to process or carry out mixing reaction with other materials, and compared with the polyvinyl chloride, the modified polyvinyl chloride has good heat resistance, acid and alkali resistance, oxidation resistance, flexibility and the like, and is further modified by an organic silicon modifier, so that the heat resistance and the flame retardance of the silica gel-like thermoplastic resin are improved;
2. through the combination of dimethyl silicone oil, phenyl silicone oil and hydroxyl silicone oil, the obtained organic silicon modifier has better flame retardance and high temperature resistance, so that the flame retardance and the high temperature resistance of the silica gel-like thermoplastic resin are improved;
3. the dioctyl phthalate, the dibutyl phthalate and the chlorinated paraffin have a synergistic effect and can play a role in plasticization, and the chlorinated paraffin has the advantages of flame retardance and electrical insulation, so that the plasticity and the flame retardance of the silica gel-like thermoplastic resin are enhanced.
Detailed Description
Preparation example
Examples of preparation of polyvinyl chloride
Preparation example 1
The preparation of polyvinyl chloride includes the following steps:
s1: weighing 5Kg of hydroxymethyl cellulose, 1Kg of calcium stearate and 150Kg of deionized water, adding into a pressure reaction kettle with a stirrer, and stirring until the hydroxymethyl cellulose and the calcium stearate are completely dissolved to obtain a mixture A for later use;
s2: weighing 5Kg of diisopropyl peroxydicarbonate and 2Kg of azobisisoheptonitrile, adding the mixture A obtained in S1, stirring uniformly, pumping out air in a pressure reaction kettle through a vacuum pump until the vacuum table shows-0.1 Mpa, and obtaining a mixture B;
s3: weighing 60Kg of chloroethylene, adding the chloroethylene into the mixture B obtained in the step S2, uniformly stirring, heating to 55 ℃, and reacting for 5 hours to obtain a mixed solution C;
s4: weighing 2Kg of sodium persulfate and 55Kg of chloroethylene, heating to 70 ℃, reacting for 3h, cooling to room temperature, adding 80% ethanol solution by mass for cleaning, putting into a centrifugal dehydrator for dehydration, putting into a 50 ℃ oven for drying, grinding, and sieving with a 200-mesh sieve to obtain the polyvinyl chloride.
Preparation example 2
The preparation of polyvinyl chloride includes the following steps:
s1: weighing 3Kg of hydroxymethyl cellulose, 0.7Kg of calcium stearate and 140Kg of deionized water, adding into a pressure reaction kettle with a stirrer together, and stirring until the hydroxymethyl cellulose and the calcium stearate are completely dissolved to obtain a mixture A for later use;
s2: weighing 4Kg of diisopropyl peroxydicarbonate and 1.5Kg of azobisisoheptonitrile, stirring uniformly, pumping out air in a pressure reaction kettle by a vacuum pump until the vacuum table shows-0.1 Mpa, and obtaining a mixture B;
s3: weighing 50Kg of chloroethylene, adding the chloroethylene into the mixture B obtained in the step S2, uniformly stirring, heating to 55 ℃, and reacting for 4 hours to obtain a mixed solution C;
s4: weighing 1.5Kg of sodium persulfate and 55Kg of chloroethylene, heating to 70 ℃, reacting for 2.5h, cooling to room temperature, adding 75% ethanol solution by mass for cleaning, putting into a centrifugal dehydrator for dehydration, putting into a 50 ℃ oven for drying, grinding, and sieving with 200 meshes to obtain the polyvinyl chloride.
Preparation example 3
The preparation of polyvinyl chloride includes the following steps:
s1: weighing 2Kg of hydroxymethyl cellulose, 0.5Kg of calcium stearate and 140Kg of deionized water, adding into a pressure reaction kettle with a stirrer together, and stirring until the hydroxymethyl cellulose and the calcium stearate are completely dissolved to obtain a mixture A for later use;
s2: weighing 3Kg of diisopropyl peroxydicarbonate and 1Kg of azobisisoheptonitrile, stirring uniformly, pumping out air in a pressure reaction kettle by a vacuum pump until the vacuum table shows-0.1 Mpa, and obtaining a mixture B;
s3: weighing 40Kg of chloroethylene, adding the chloroethylene into the mixture B obtained in the step S2, uniformly stirring, heating to 45 ℃, and reacting for 3 hours to obtain a mixed solution C;
s4: weighing 1Kg of sodium persulfate and 50Kg of chloroethylene, heating to 60 ℃, reacting for 2h, cooling to room temperature, adding 70% ethanol solution by mass for cleaning, putting into a centrifugal dehydrator for dehydration, putting into a 50 ℃ oven for drying, grinding, and sieving with a 200-mesh sieve to obtain the polyvinyl chloride.
Preparation example of modified polyvinyl chloride
Preparation example 4
The preparation method of the modified polyvinyl chloride comprises the following steps:
step 1: weighing 90Kg of polyvinyl chloride obtained in the preparation example 1 and 180Kg of water, and uniformly mixing to obtain a mixture I;
step 2: weighing 5Kg of lauroyl peroxide, 2Kg of glyceryl monostearate and 3Kg of dimethyltin dichloride, adding the mixture I obtained in the step 1 and the mixture I into a chlorination reaction kettle, uniformly mixing, pumping out air in the pressure reaction kettle by a vacuum pump until the vacuum table shows-0.1 Mpa, and obtaining a mixture II;
and step 3: adding chlorine into the mixture II obtained in the step 2, pressurizing to 1.3Mpa, and reacting for 3h at 60 ℃ to obtain a mixture III;
and 4, step 4: and (3) irradiating the mixture III obtained in the step (3) by using an ultraviolet lamp, heating to 80 ℃, reacting for 5 hours, stopping adding chlorine, cooling to room temperature, adding a sodium hydroxide solution with the mass fraction of 8% for neutralization, washing by using deionized water, putting into a centrifugal dehydrator for dehydration, putting into a 50 ℃ oven for drying, grinding, and sieving by using a 150-mesh sieve to obtain the modified polyvinyl chloride.
Preparation example 5
The preparation method of the modified polyvinyl chloride comprises the following steps:
step 1: weighing 100Kg of polyvinyl chloride obtained in the preparation example 2 and 200Kg of water, and uniformly mixing to obtain a mixture I;
step 2: weighing 4Kg of lauroyl peroxide, 1.5Kg of glyceryl monostearate and 2Kg of dimethyltin dichloride, adding the mixture I obtained in the step 1 and the mixture I into a chlorination reaction kettle, uniformly mixing, pumping out air in the pressure reaction kettle by a vacuum pump until the vacuum table shows-0.1 Mpa, and obtaining a mixture II;
and step 3: adding chlorine into the mixture II obtained in the step 2, pressurizing to 1.3Mpa, and reacting for 2h at 55 ℃ to obtain a mixture III;
and 4, step 4: and (3) irradiating the mixture III obtained in the step (3) by using an ultraviolet lamp, heating to 75 ℃, reacting for 4 hours, stopping adding chlorine, cooling to room temperature, adding a sodium hydroxide solution with the mass fraction of 6% for neutralization, washing by using deionized water, putting into a centrifugal dehydrator for dehydration, putting into a 50 ℃ oven for drying, grinding, and sieving by using a 130-mesh sieve to obtain the modified polyvinyl chloride.
Preparation example 6
Step 1: weighing 80Kg of polyvinyl chloride obtained in the preparation example 3 and 100Kg of water, and uniformly mixing to obtain a mixture I;
step 2: weighing 3Kg of lauroyl peroxide, 1Kg of glyceryl monostearate and 1Kg of dimethyltin dichloride, adding the mixture I obtained in the step 1 into a chlorination reaction kettle, uniformly mixing, pumping out air in the pressure reaction kettle by a vacuum pump until the vacuum table shows-0.1 Mpa, and obtaining a mixture II;
and step 3: adding chlorine into the mixture II obtained in the step 2, pressurizing to 1.3Mpa, and reacting for 2h at 50 ℃ to obtain a mixture III;
and 4, step 4: and (3) irradiating the mixture III obtained in the step (3) by using an ultraviolet lamp, heating to 70 ℃, reacting for 3 hours, stopping adding chlorine, cooling to room temperature, adding a sodium hydroxide solution with the mass fraction of 5% for neutralization, washing by using deionized water, putting into a centrifugal dehydrator for dehydration, putting into a 50 ℃ oven for drying, grinding and sieving by a 100-mesh sieve to obtain the modified polyvinyl chloride.
Preparation example 7
The preparation method of the modified polyvinyl chloride comprises the following steps:
step 1: weighing 100Kg of polyvinyl chloride sold in the market and 200Kg of water, and uniformly mixing to obtain a mixture I;
step 2: weighing 4Kg of lauroyl peroxide, 1.5Kg of glyceryl monostearate and 2Kg of dimethyltin dichloride, adding the mixture I obtained in the step 1 and the mixture I into a chlorination reaction kettle, uniformly mixing, pumping out air in the pressure reaction kettle by a vacuum pump until the vacuum table shows-0.1 Mpa, and obtaining a mixture II;
and step 3: adding chlorine into the mixture II obtained in the step 2, pressurizing to 1.3Mpa, and reacting for 2h at 55 ℃ to obtain a mixture III;
and 4, step 4: and (3) irradiating the mixture III obtained in the step (3) by using an ultraviolet lamp, heating to 75 ℃, reacting for 4 hours, stopping adding chlorine, cooling to room temperature, adding a sodium hydroxide solution with the mass fraction of 6% for neutralization, washing by using deionized water, putting into a centrifugal dehydrator for dehydration, putting into a 50 ℃ oven for drying, grinding, and sieving by using a 130-mesh sieve to obtain the modified polyvinyl chloride.
Examples
Example 1
A preparation method of the silica gel-like thermoplastic resin comprises the following steps:
step A: weighing 100Kg of modified polyvinyl chloride, 1Kg of dioctyl phthalate, 2Kg of dibutyl phthalate and 5Kg of chlorinated paraffin, and uniformly mixing to obtain a mixture 1;
and B: weighing 2Kg of dimethyl silicone oil, 8Kg of phenyl silicone oil, 10Kg of hydroxyl silicone oil, 5Kg of paraffin oil, 3Kg of antimony trioxide, 2Kg of zinc borate, 1Kg of fumed silica, 1.5Kg of kaolin and 2Kg of nano-silica, uniformly mixing, adding the mixture 1 obtained in the step A into a double-roll plasticator, mixing for 15 minutes at 160 ℃, and performing injection molding through an injection molding machine at 185 ℃ to obtain the silica-like thermoplastic resin.
Examples 2 to 8
Examples 2-8 differ from example 1 above in the type and amount of material used, as shown in table 1 below:
TABLE 1 EXAMPLES 1-8 Contents of respective raw materials
Comparative example
Comparative example 1
Comparative example 1 differs from example 5 in that the modified polyvinyl chloride in the raw material was replaced with an acrylic resin in equal amounts.
Comparative example 2
Comparative example 2 differs from example 4 in that the silicone modifier in the starting material was replaced with an equal amount of ethyl silicone oil.
Performance test
The data for examples 1-8 and comparative examples 1-2 are shown in Table 2.
Performance test method
1. Tensile breaking strength and tensile breaking elongation
Testing according to the national standard GB/T1040;
2. oxygen index and flame retardant rating
The oxygen index is tested according to the national standard GBT24093, and the flame retardant grade is tested according to the national standard ANSI/UL-94-1985; the results of the performance tests of the silicone-like thermoplastic resins of examples 1-8 and comparative examples 1-2 are shown in Table 2:
TABLE 2 test data for examples 1-8 and comparative examples 1-2
It can be seen from the combination of examples 3-8 and example 1 and table 2 that the tensile strength at break, tensile elongation at break and oxygen index of examples 3-8 are all higher than those of example 1, which shows that the polyvinyl chloride obtained by adding the polyvinyl chloride prepared by the preparation method of the present application in examples 3-8 has higher content than that of the commercially available polyvinyl chloride, so that the obtained modified polyvinyl chloride has higher purity, and further, after being mixed with other raw materials, the obtained silicone-like thermoplastic resin has better flexibility, flame retardance and the like.
As can be seen by combining examples 3-8 and example 2 and table 2, the tensile breaking strength, tensile breaking elongation and oxygen index of examples 3-8 are all higher than those of example 2, which shows that the modified polyvinyl chloride obtained by adding the modified polyvinyl chloride prepared by the preparation method of the application of examples 3-8 is higher than that of the commercial modified polyvinyl chloride, and further, the silicone-like thermoplastic resin with better flexibility, flame retardance and high temperature resistance is obtained.
Combining example 5 and comparative example 1 and table 2, it can be seen that tensile breaking strength, tensile breaking elongation and oxygen index of example 5 are all higher than those of comparative example 1, and the flame retardant rating of comparative example 1 is higher than that of example 5, which indicates that the flame retardant effect of the silicone-like thermoplastic resin obtained by acrylic resin in comparative example 1 is poorer than that of the silicone-like thermoplastic resin obtained by modified polyvinyl chloride in example 5, and further indicates that the silicone-like thermoplastic resin obtained by composite modification of modified polyvinyl chloride has better flame retardancy, flexibility and high temperature resistance.
Combining example 4 and comparative example 2 and table 2, it can be seen that the tensile breaking strength, tensile breaking elongation and oxygen index of example 4 are all higher than those of comparative example 2, and the flame retardant rating of comparative example 2 is higher than that of example 4, which shows that the silicone-like thermoplastic resin obtained by adding the silicone modifier of example 4 has better flame retardancy, flexibility and high temperature resistance than the silicone-like thermoplastic resin obtained by adding the ethyl silicone oil of comparative example 2, and further shows that the silicone-like thermoplastic resin obtained by adding the silicone modifier has better flexibility, flame retardancy and high temperature resistance.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The silica gel-like thermoplastic resin is characterized by being prepared from the following raw materials in parts by weight:
modified polyvinyl chloride: 80 to 100 portions of
Silicone modifier: 5-30 parts of
Paraffin oil: 3-8 parts of
Plasticizer: 5-10 parts of
Flame retardant: 4 to 7 portions of
Filling agent: 2-5 parts.
2. The silicone-like thermoplastic resin of claim 1, wherein: the preparation of the modified polyvinyl chloride comprises the following steps:
step 1: weighing 80-100 parts by weight of polyvinyl chloride and 150-200 parts by weight of water, and uniformly mixing to obtain a mixture I;
step 2: weighing 3-5 parts by weight of lauroyl peroxide, 1-2 parts by weight of glyceryl monostearate and 1-3 parts by weight of dimethyltin dichloride, adding into the mixture I obtained in the step 1, uniformly mixing, and vacuumizing to obtain a mixture II;
and step 3: introducing chlorine into the mixture II obtained in the step 2, pressurizing, heating to 50-60 ℃, and reacting for 2-3h to obtain a mixture III;
and 4, step 4: and (3) irradiating the mixture III obtained in the step (3) by using ultraviolet, heating to 70-80 ℃, reacting for 3-5h, cooling, adding a sodium hydroxide solution with the mass fraction of 5-8% for neutralization, washing with water, drying, grinding, and sieving by using a sieve of 100 meshes and 150 meshes to obtain the modified polyvinyl chloride.
3. The silicone-like thermoplastic resin of claim 2, wherein: the preparation of the polyvinyl chloride comprises the following steps:
s1: weighing 2-5 parts by weight of hydroxymethyl cellulose and 0.5-1 part by weight of calcium stearate, dissolving in 150 parts by weight of water, and uniformly stirring to obtain a mixture A for later use;
s2: weighing 3-5 parts by weight of diisopropyl peroxydicarbonate and 1-2 parts by weight of azobisisoheptonitrile, adding into the mixture A obtained in S1, stirring uniformly, and pumping air to obtain a mixture B;
s3: weighing 40-60 parts by weight of chloroethylene, adding the chloroethylene into the mixture B obtained in the step S2, uniformly stirring, heating to 45-55 ℃, and reacting for 3-5 hours to obtain a mixed solution C;
s4: weighing 1-2 parts by weight of sodium persulfate and 50-60 parts by weight of chloroethylene, heating to 60-75 ℃, reacting for 2-3h, cooling to room temperature, adding 70-80% by mass of ethanol solution for cleaning, dehydrating, drying, grinding, and sieving by a sieve of 100 meshes and 200 meshes to obtain the polyvinyl chloride.
4. The silicone-like thermoplastic resin of claim 1, wherein: the plasticizer is composed of one or more of dioctyl phthalate, dibutyl phthalate and chlorinated paraffin.
5. The silicone-like thermoplastic resin of claim 1, wherein: the organic silicon modifier is formed by mixing dimethyl silicone oil, phenyl silicone oil and hydroxyl silicone oil.
6. The silicone-like thermoplastic resin of claim 5, wherein: the weight ratio of the dimethyl silicone oil to the phenyl silicone oil to the hydroxyl silicone oil is 1: 2-5: 3-8.
7. The silicone-like thermoplastic resin of claim 1, wherein: the flame retardant is antimony trioxide and/or zinc borate.
8. The silicone-like thermoplastic resin of claim 1, wherein: the filler is one or a combination of more of fumed silica, kaolin and nano silicon dioxide.
9. The silicone-like thermoplastic resin of claim 8, wherein: the kaolin, the nano silicon dioxide and the fumed silica are in a weight ratio of 1:1-2: 1-3.
10. A method of preparing the silicone-like thermoplastic resin of any one of claims 1-9, comprising the steps of:
step A: weighing 80-100 parts by weight of modified polyvinyl chloride and 5-10 parts by weight of plasticizer, and uniformly mixing to obtain a mixture 1;
step B: and (2) weighing 5-30 parts by weight of an organic silicon modifier, 3-8 parts by weight of paraffin oil, 4-7 parts by weight of a flame retardant and 2-5 parts by weight of a filler, adding the mixture into the mixture 1 obtained in the step A, uniformly stirring, heating to 155-165 ℃, mixing for 5-15 minutes, and performing injection molding through an injection molding machine at 185 ℃ to obtain the silica gel-like thermoplastic resin.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008063577A (en) * | 2006-09-05 | 2008-03-21 | Chitec Technology Co Ltd | Biodegradable resin composition improved in toughness and heat resistance, and method for manufacturing biodegradable resin |
| CN104403227A (en) * | 2014-11-14 | 2015-03-11 | 宁波一舟塑胶有限公司 | Silica gel-like flame-retardant polyvinyl chloride plastic |
| KR20170008176A (en) * | 2015-07-13 | 2017-01-23 | 히타치 긴조쿠 가부시키가이샤 | Pvc composition, as well as electric wire and cable using the same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008063577A (en) * | 2006-09-05 | 2008-03-21 | Chitec Technology Co Ltd | Biodegradable resin composition improved in toughness and heat resistance, and method for manufacturing biodegradable resin |
| CN104403227A (en) * | 2014-11-14 | 2015-03-11 | 宁波一舟塑胶有限公司 | Silica gel-like flame-retardant polyvinyl chloride plastic |
| KR20170008176A (en) * | 2015-07-13 | 2017-01-23 | 히타치 긴조쿠 가부시키가이샤 | Pvc composition, as well as electric wire and cable using the same |
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