CN114685911A - Thermal stability PVC and preparation method and application thereof - Google Patents
Thermal stability PVC and preparation method and application thereof Download PDFInfo
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- CN114685911A CN114685911A CN202210266113.0A CN202210266113A CN114685911A CN 114685911 A CN114685911 A CN 114685911A CN 202210266113 A CN202210266113 A CN 202210266113A CN 114685911 A CN114685911 A CN 114685911A
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- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 50
- 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 19
- 239000003063 flame retardant Substances 0.000 claims abstract description 19
- 239000000945 filler Substances 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000004800 polyvinyl chloride Substances 0.000 claims description 89
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 89
- 238000002156 mixing Methods 0.000 claims description 30
- 239000003963 antioxidant agent Substances 0.000 claims description 25
- 230000003078 antioxidant effect Effects 0.000 claims description 23
- 239000000314 lubricant Substances 0.000 claims description 20
- 239000012745 toughening agent Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 14
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 14
- 238000006116 polymerization reaction Methods 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
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920001897 terpolymer Polymers 0.000 claims description 3
- 239000004801 Chlorinated PVC Substances 0.000 claims description 2
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 54
- 238000000354 decomposition reaction Methods 0.000 abstract description 15
- 239000000155 melt Substances 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 20
- 239000011347 resin Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000011812 mixed powder Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 9
- 239000000498 cooling water Substances 0.000 description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- -1 n-octyl Chemical group 0.000 description 4
- HENMSNJYDGNBMU-UHFFFAOYSA-M calcium;zinc;octadecanoate Chemical compound [Ca+2].[Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O HENMSNJYDGNBMU-UHFFFAOYSA-M 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003017 thermal stabilizer Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- PZGVVCOOWYSSGB-UHFFFAOYSA-L but-2-enedioate;dioctyltin(2+) Chemical compound CCCCCCCC[Sn]1(CCCCCCCC)OC(=O)C=CC(=O)O1 PZGVVCOOWYSSGB-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002688 maleic acid derivatives Chemical class 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- IQBLWPLYPNOTJC-FPLPWBNLSA-N (z)-4-(2-ethylhexoxy)-4-oxobut-2-enoic acid Chemical compound CCCCC(CC)COC(=O)\C=C/C(O)=O IQBLWPLYPNOTJC-FPLPWBNLSA-N 0.000 description 1
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- YAHBZWSDRFSFOO-UHFFFAOYSA-L dimethyltin(2+);2-(2-ethylhexoxy)-2-oxoethanethiolate Chemical compound CCCCC(CC)COC(=O)CS[Sn](C)(C)SCC(=O)OCC(CC)CCCC YAHBZWSDRFSFOO-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- C08L27/02—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 not modified by chemical after-treatment
- C08L27/04—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 not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Abstract
The invention discloses a thermal stability PVC and a preparation method and application thereof, belonging to the technical field of polymer modified materials. The thermal stability PVC comprises, by weight, 100 parts of PVC, 2.5-5.5 parts of a heat stabilizer, 3-8 parts of a flame retardant, 5-12 parts of a flexibilizer, 5-20 parts of a filler and 0-4 parts of other auxiliaries. The thermal stability PVC of the invention obviously improves the thermal stability and the fluidity of PVC through the synergistic effect of the composite heat stabilizer and other components, has excellent thermal stability, the initial decomposition temperature of more than 240 ℃, and the PVC material also has good fluidity, the melt flow rate of more than 57g/10min, can meet the requirements of thermal stability and fluidity for PVC materials in the fields of automobile manufacture and electronic appliances, and can be widely applied in the fields of automobile manufacture and electronic appliances.
Description
Technical Field
The invention relates to the technical field of high polymer modified materials, and particularly relates to thermal stability PVC and a preparation method and application thereof.
Background
The PVC material has the advantages of flame retardance, strong rigidity, corrosion resistance and the like, has large modification span, can be changed from soft to hard, and can be changed from transparent to opaque, so the PVC material has wide application range and can be applied to the fields of automobile manufacturing, electronic appliances and the like for a long time. The biggest disadvantage of PVC is poor thermal stability, so that a thermal stabilizer must be added in the using process, and the unmodified PVC resin is useless. The main reason for poor thermal stability of PVC materials is that PVC resins contain a large number of unstable structures, such as double bonds, free chlorine atoms, allyl chloride, and the like, which are easily decomposed during processing to generate hydrogen chloride, which promotes further decomposition of PVC, resulting in loss of performance and use value of the materials.
The prior art discloses a PVC composite heat stabilizer, which contains organic tin, terephthalic acid metal salt, lubricant, phosphite ester and beta-diketone compound, wherein the organic tin is selected from one or more of methyl tin mercaptide, dibutyl tin dilaurate, dioctyl tin dilaurate, dibutyl tin maleate, dioctyl tin maleate, di-n-octyl tin maleate, di-n-butyl tin bis (mono-octyl maleate) and n-octyl bis (isooctyl mercaptide) tin. The heat stabilizer mainly aims to overcome the defects of toxicity, poor colorability, short heat stabilization time, high price, odor and the like of the traditional heat stabilizer, has good compatibility and easy dispersion when being added into PVC for processing, and cannot cause stickiness to cause processing difficulty. However, the improvement of the thermal stability of the PVC is limited, the PVC can only have the thermal stability in the environment of 180 +/-1 ℃, the thermal decomposition temperature is not high, and the fluidity of the PVC is not improved.
Disclosure of Invention
The invention aims to overcome the defect and the defect of poor thermal stability of the existing PVC material, and provides the thermal stability PVC.
Another object of the present invention is to provide a method for preparing a PVC having thermal stability.
The invention also aims to provide application of the thermal stability PVC in the fields of automobile manufacturing and electronic and electric appliances.
The above purpose of the invention is realized by the following technical scheme:
the thermal stability PVC comprises the following components in parts by weight:
100 parts of PVC, 2.5-5.5 parts of heat stabilizer, 3-8 parts of flame retardant, 5-12 parts of toughener, 5-20 parts of filler and 0-4 parts of other auxiliary agents,
the heat stabilizer is a composite heat stabilizer of mercaptan organic tin and maleic acid organic tin, wherein the mercaptan organic tin accounts for 1.5-3 parts, and the maleic acid organic tin accounts for 1-2.5 parts.
Among them, it should be noted that:
mercaptan organotin and maleic acid organotin are used as heat stabilizers, wherein the mercaptan organotin plays a role in replacing unstable chlorine atoms in PVC, and the maleic acid organotin plays a role in reacting with unstable double bond structures in materials to inhibit the coloring of the materials. After the two materials are cooperated, the thermal stability of the material can be improved, the decomposition and agglomeration probability of the PVC material is reduced, and the fluidity of the material is improved. If the usage amount of the organic tin heat stabilizer is too small, the heat stability of the PVC material cannot be guaranteed, but the usage amount of the heat stabilizer has an upper limit on the promotion effect of the heat stability of the material, and if the usage amount is too large, the useless cost is increased.
The filler of the invention can be one or more of calcium carbonate, barium sulfate or kaolin.
In order to further improve the thermal stability and the fluidity of the PVC material, preferably, the organotin mercaptide is 2 to 2.5 parts, and the organotin maleate is 1.5 to 2.2 parts.
In a specific embodiment, the polymerization degree of the PVC is preferably 400-800.
Among them, it should be noted that:
the polymerization degree of the PVC is detected according to the GB/T5761-2006 standard.
The polymerization degree of PVC has certain influence on the fluidity of the material, and the polymerization degree value is further optimized to remarkably improve the fluidity of the thermal stability PVC.
In a specific embodiment, in order to meet other performances or processing requirements of the PVC material, the other auxiliary agents comprise an antioxidant and a lubricant, and the mass ratio of the antioxidant to the lubricant is 1: 2-4.
Wherein the antioxidant can be one or more of hindered phenol antioxidant, phosphite antioxidant and thioester antioxidant.
The lubricant may be one or more of polyethylene wax, stearic acid, and paraffin wax.
In a specific embodiment, the flame retardant of the present invention is one or more of antimony trioxide, hydroxide or phosphate.
In a specific embodiment, the toughening agent is one or two of chlorinated polyvinyl chloride and methyl methacrylate-butadiene-styrene terpolymer.
The invention also specifically protects a preparation method of the PVC with thermal stability, which comprises the following steps:
s1, uniformly mixing the raw material components except the filler at a low speed;
s2, adding a filler, and mixing at a high speed to obtain a mixture;
and S3, extruding the mixture by adopting a double-stage double-screw extruder to obtain the heat-stable PVC.
Among them, it should be noted that:
the mixing speed of the low-speed mixing in the invention is as follows: 20-40 revolutions/s
The mixing speed of the high-speed mixing in the invention is as follows: 60-100 revolutions/s
The PVC resin is decomposed at a high temperature, and the components are mixed at a low speed at S1 to prevent the material temperature from suddenly rising, resulting in the decomposition of PVC.
And (3) placing the slurry after high-speed mixing into a cooling cylinder with a circulating cooling water device, and obtaining a mixture after the temperature reaches 60-80 ℃.
The application of the thermal stability PVC in the fields of automobile manufacturing and electronic and electric appliances is also within the protection scope of the invention.
The PVC material has excellent thermal stability, the initial decomposition temperature can reach more than 240 ℃, the PVC material also has good fluidity, the melt mass flow rate can reach more than 57g/10min, the thermal stability and fluidity requirements of the PVC material in the fields of automobile manufacturing and electronic appliances can be met, and the PVC material can be widely applied to the fields of automobile manufacturing and electronic appliances.
The invention also specifically protects a thermal stability plastic product prepared from the thermal stability PVC.
Compared with the prior art, the invention has the beneficial effects that:
the heat stabilizer of the heat-stable PVC is a composite heat stabilizer of mercaptan organotin and organotin maleate, obviously improves the heat stability and the fluidity of PVC through the synergistic effect of the composite heat stabilizer and other components, has excellent heat stability, has the initial decomposition temperature of over 240 ℃, has good fluidity for PVC materials, has the melt mass flow rate of over 57g/10min, can meet the requirements of heat stability and fluidity for PVC materials in the fields of automobile manufacture and electronic and electrical appliances, and can be widely applied to the fields of automobile manufacture and electronic and electrical appliances.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
The raw materials for the examples and comparative examples of the present invention are illustrated below:
PVC resin-1: the polymerization degree is 500, the trade name is PVC S-50, and the PVC is purchased from Tai plastic industry Co.Ltd;
PVC resin-2: the polymerization degree is 1000, the mark number is PVC TL-1000, and the product is purchased from Tianjin le gold Bohai chemical company, Inc.;
thermal stabilizer:
thermal stabilizer a: organotin mercaptide, designation YT-181, manufactured by Yunnan tin group Limited liability company;
and (3) heat stabilizer B: organotin maleate, designation DX-650, manufacturer's thoroughfare, Jianhuadong, Asahi adjuvant, Inc.;
and (3) a heat stabilizer C: calcium zinc stearate heat stabilizer, designation RUP-110C, manufacturer addicaceae investment ltd;
and (3) a heat stabilizer D: hindered amine and phosphorus-nitrogen compound composite heat stabilizer, trade mark SA-560, the manufacturer has all opened the high-energy chemical industry Limited company;
flame retardant: antimony trioxide: commercially available, the examples of the invention and comparative examples are all of the same species;
a toughening agent: methylmethacrylate-butadiene-styrene terpolymer, commercially available, the examples of the present invention and the comparative examples are all the same commercially available product;
filling agent: calcium carbonate, commercially available, the examples of the invention and the comparative examples are all the same commercially available product;
antioxidant: hindered phenolic antioxidants, commercially available, the examples and comparative examples of the present invention are all the same commercially available product;
lubricant: polyethylene wax, commercially available, and the examples of the invention and comparative examples are all the same commercially available product.
Examples 1 to 8
The thermal stability PVC comprises the following components in parts by weight as shown in the following table 1.
TABLE 1PVC raw Material composition
The preparation method of the PVC material of the embodiment 1-8 comprises the following steps:
s1, weighing PVC resin, a heat stabilizer, a flame retardant, a toughening agent, a lubricant and an antioxidant according to a ratio, placing the PVC resin, the heat stabilizer, the flame retardant, the toughening agent, the lubricant and the antioxidant into a high-speed mixer with an exhaust port, heating and mixing at a low speed, wherein the mixing speed is 30 revolutions per second;
s2, weighing the filling agent according to the proportion, starting high-speed mixing, discharging the mixture into a cold cylinder with a circulating cooling water device when the mixed powder reaches a certain material temperature, and obtaining a mixed material after the mixed powder reaches the certain material temperature, wherein the high-speed mixing speed is 80 revolutions per second;
and S3, extruding the mixture obtained in the step 2) by using a double-stage double-screw extruder to obtain a finished product.
Example 9
The PVC material comprises the following components in parts by weight
100 parts of PVC, 2.1 parts of heat stabilizer A, 1.8 parts of heat stabilizer B, 6 parts of flame retardant, 8 parts of toughener, 10 parts of filler, 0.4 part of antioxidant and 1.2 parts of lubricant,
the difference from example 3 is that the PVC is PVC-2.
The preparation method of the PVC material comprises the following steps:
s1, weighing PVC resin, a heat stabilizer, a flame retardant, a toughening agent, a lubricant and an antioxidant according to a ratio, placing the PVC resin, the heat stabilizer, the flame retardant, the toughening agent, the lubricant and the antioxidant into a high-speed mixer with an exhaust port, heating and mixing at a low speed, wherein the mixing speed is 30 revolutions per second;
s2, weighing the filling agent according to the proportion, starting high-speed mixing, discharging the mixture into a cold cylinder with a circulating cooling water device when the mixed powder reaches a certain material temperature, and obtaining a mixed material after the mixed powder reaches the certain material temperature, wherein the high-speed mixing speed is 80 revolutions per second;
and S3, extruding the mixture obtained in the step S2 by using a double-stage double-screw extruder to obtain a finished product.
Comparative example 1
The PVC material comprises the following components in parts by weight
100 parts of PVC, 5.5 parts of heat stabilizer, 6 parts of flame retardant, 8 parts of toughener, 10 parts of filler, 0.4 part of antioxidant and 1.2 parts of lubricant,
the difference from example 3 is that the heat stabilizer is 5.5 parts organotin mercaptide.
The preparation method of the PVC material comprises the following steps:
s1, weighing PVC resin, a heat stabilizer, a flame retardant, a toughening agent, a lubricant and an antioxidant according to a ratio, placing the PVC resin, the heat stabilizer, the flame retardant, the toughening agent, the lubricant and the antioxidant into a high-speed mixer with an exhaust port, heating and mixing at a low speed, wherein the mixing speed is 30 revolutions per second;
s2, weighing the filling agent according to the proportion, starting high-speed mixing, discharging the mixture into a cold cylinder with a circulating cooling water device when the mixed powder reaches a certain material temperature, and obtaining a mixed material after the mixed powder reaches the certain material temperature, wherein the high-speed mixing speed is 80 revolutions per second;
and S3, extruding the mixture obtained in the step 2) by using a double-stage double-screw extruder to obtain a finished product.
Comparative example 2
The PVC material comprises the following components in parts by weight
100 parts of PVC, 5.5 parts of heat stabilizer, 6 parts of flame retardant, 8 parts of toughener, 10 parts of filler, 0.4 part of antioxidant and 1.2 parts of lubricant,
the difference from example 3 is that the heat stabilizer is 5.5 parts of organotin maleate.
The preparation method of the PVC material comprises the following steps:
s1, weighing PVC resin, a heat stabilizer, a flame retardant, a toughening agent, a lubricant and an antioxidant according to a ratio, placing the PVC resin, the heat stabilizer, the flame retardant, the toughening agent, the lubricant and the antioxidant into a high-speed mixer with an exhaust port, heating and mixing at a low speed, wherein the mixing speed is 30 revolutions per second;
s2, weighing the filling agent according to the proportion, starting high-speed mixing, discharging the mixture into a cold cylinder with a circulating cooling water device when the mixed powder reaches a certain material temperature, and obtaining a mixed material after the mixed powder reaches the certain material temperature, wherein the high-speed mixing speed is 80 revolutions per second;
and S3, extruding the mixture obtained in the step 2) by using a double-stage double-screw extruder to obtain a finished product.
Comparative examples 3 to 9
A PVC material comprises the following components in parts by weight:
TABLE 2 comparative examples the contents of the components
The preparation method of the PVC material of comparative examples 3-9 comprises the following steps:
s1, weighing PVC resin, a heat stabilizer, a flame retardant, a toughening agent, a lubricant and an antioxidant according to a ratio, placing the PVC resin, the heat stabilizer, the flame retardant, the toughening agent, the lubricant and the antioxidant in a high-speed mixer with an exhaust port, heating and mixing at a low speed, wherein the mixing speed is 40 revolutions per second;
s2, weighing the fillers according to the proportion, starting high-speed mixing, discharging the mixture into a cooling cylinder with a circulating cooling water device when the mixed powder reaches a certain material temperature through high-speed mixing, and obtaining a mixed material after the mixed powder reaches the certain material temperature, wherein the high-speed mixing speed is 100 revolutions per minute;
and S3, extruding the mixture obtained in the step 2) by using a double-stage double-screw extruder to obtain a finished product.
Result detection
(1) Thermal stability
The thermal stability of the examples and comparative examples was evaluated using the initial decomposition temperature of the material as an index, and the test apparatus was a NETZSCH thermogravimetric analyzer, model TG 209F 1. The test method is nitrogen atmosphere, the temperature is raised from normal temperature to 750 ℃ at the temperature raising speed of 20 ℃/min and then is stopped, and the temperature of 1% mass decomposition of the recording material is the initial decomposition temperature.
(2) Fluidity of the resin
The fluidity of examples and comparative examples was evaluated by the melt flow rate, ASTM D1238, under the conditions of a temperature of 210 ℃ and a load of 10 Kg.
The specific test results are shown in Table 3 below.
TABLE 3 results of fluidity and thermal stability test
As can be seen from the data in the above Table 3, the thermal stability PVC of the present invention has good thermal stability, the initial decomposition temperature of 1% of the mass decomposition can reach above 240 ℃, the thermal stability PVC also has good fluidity, the melt flow rate can reach 57g/10min, the thermal stability and fluidity requirements of PVC materials in the fields of automobile manufacture and electronic appliances can be satisfied, and the present invention can be widely applied in the fields of automobile manufacture and electronic appliances.
In comparative example 1 in which only organotin mercaptide was used as a heat stabilizer and in comparative example 2 in which only organotin maleate was used as a heat stabilizer, the initial decomposition temperature at which 1% of the heat stability mass decomposition could not reach 240 ℃.
In comparative examples 3 and 4, although the heat stabilizer is a composite heat stabilizer of organotin mercaptides and organotin maleates, the content of the organotin maleates is too high or too low, and the corresponding heat stability can not meet the relevant requirements.
In comparative examples 5 and 6, although the heat stabilizer is a composite heat stabilizer of organotin mercaptide and organotin maleate, the content of organotin mercaptide is too high or too low, and the corresponding heat stability performance can not reach the relevant requirements.
Comparative example 7 adopts organotin maleate and calcium zinc stearate as composite heat stabilizers, comparative example 8 adopts organotin mercaptide and calcium zinc stearate as composite heat stabilizers, and comparative example 9 adopts hindered amine and phosphorus-nitrogen compound composite heat stabilizers, but the initial decomposition temperature of 1% of mass decomposition of the heat stabilizers can not reach more than 240 ℃, obviously, the corresponding heat stability performance of the heat stabilizers cannot reach related requirements after the heat stabilizers are compounded, the flowability of PVC is not good, the melt flow rate can not reach 57g/10min, the technical problem of the invention can not be solved, and the application requirements in the fields of automobile manufacturing and electronic and electrical appliances can not be met.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The thermal stability PVC is characterized by comprising the following components in parts by weight:
100 parts of PVC, 2.5-5.5 parts of heat stabilizer, 3-8 parts of flame retardant, 5-12 parts of toughener, 5-20 parts of filler and 0-4 parts of other auxiliary agents,
the heat stabilizer is a composite heat stabilizer of organotin mercaptide and organotin maleate, wherein the organotin mercaptide accounts for 1.5-3 parts, and the organotin maleate accounts for 1-2.5 parts.
2. The thermally stable PVC of claim 1, wherein the organotin mercaptide is 2 to 2.5 parts and the organotin maleate is 1.5 to 2.2 parts.
3. The thermally stable PVC of claim 1, wherein the degree of polymerization of the PVC is from 400 to 800.
4. The thermally stable PVC according to claim 1, wherein the other auxiliary agents comprise an antioxidant and a lubricant, and the mass ratio of the antioxidant to the lubricant is 1: 2-4.
5. The thermally stable PVC of claim 3, wherein the antioxidant is one or more of hindered phenolic antioxidants, phosphite antioxidants, and thioester antioxidants.
6. The thermally stable PVC of claim 1, wherein the flame retardant is antimony trioxide.
7. The thermally stable PVC of claim 1, wherein the toughening agent is one or more of chlorinated polyvinyl chloride and methylmethacrylate-butadiene-styrene terpolymer.
8. A method for preparing the thermal stability PVC according to any one of claims 1 to 7, characterized by comprising the following steps:
s1, uniformly mixing the raw material components except the filler at a low speed;
s2, adding a filler, and mixing at a high speed to obtain a mixture;
and S3, extruding the mixture by a double-stage double-screw extruder to obtain the heat-stable PVC.
9. Use of the thermally stable PVC according to any of claims 1 to 7 in the fields of automobile manufacture, electronics and electrical equipment.
10. A thermally stable plastic part, characterized in that it is prepared from a thermally stable PVC according to any of claims 1 to 7.
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| GB1225737A (en) * | 1968-07-11 | 1971-03-24 | ||
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| CN103122109A (en) * | 2013-01-16 | 2013-05-29 | 江苏爱特恩高分子材料有限公司 | PVC (polyvinyl chloride) composite heat stabilizer and application thereof |
| CN110922696A (en) * | 2019-12-06 | 2020-03-27 | 台州联成化工有限公司 | Zinc-based tin liquid heat stabilizer and preparation method thereof |
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2022
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB1225737A (en) * | 1968-07-11 | 1971-03-24 | ||
| KR19990061565A (en) * | 1997-12-31 | 1999-07-26 | 이종학 | PVC composition with excellent vacuum molding and its manufacturing method |
| CN103122109A (en) * | 2013-01-16 | 2013-05-29 | 江苏爱特恩高分子材料有限公司 | PVC (polyvinyl chloride) composite heat stabilizer and application thereof |
| CN110922696A (en) * | 2019-12-06 | 2020-03-27 | 台州联成化工有限公司 | Zinc-based tin liquid heat stabilizer and preparation method thereof |
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| 张先亮等编: "《精细化学品化学（第三版）》", pages: 251 - 252 * |
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