CN108383861B - Zinc-containing complex, preparation method thereof and plastic auxiliary agent containing zinc-containing complex - Google Patents
Zinc-containing complex, preparation method thereof and plastic auxiliary agent containing zinc-containing complex Download PDFInfo
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- CN108383861B CN108383861B CN201810148914.0A CN201810148914A CN108383861B CN 108383861 B CN108383861 B CN 108383861B CN 201810148914 A CN201810148914 A CN 201810148914A CN 108383861 B CN108383861 B CN 108383861B
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000011701 zinc Substances 0.000 title claims abstract description 79
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 78
- 229920003023 plastic Polymers 0.000 title claims abstract description 18
- 239000004033 plastic Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000012752 auxiliary agent Substances 0.000 title abstract description 14
- 239000004597 plastic additive Substances 0.000 claims abstract description 31
- 239000004593 Epoxy Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- -1 imidazole compound Chemical class 0.000 claims abstract description 17
- 150000004668 long chain fatty acids Chemical class 0.000 claims abstract description 14
- 229920005862 polyol Polymers 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 6
- LRQGFQDEQPZDQC-UHFFFAOYSA-N 1-Phenyl-1,3-eicosanedione Chemical group CCCCCCCCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 LRQGFQDEQPZDQC-UHFFFAOYSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- 235000019486 Sunflower oil Nutrition 0.000 claims description 3
- 239000002671 adjuvant Substances 0.000 claims description 3
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- 239000002600 sunflower oil Substances 0.000 claims description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 45
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 45
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 36
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 abstract description 12
- NTYJJOPFIAHURM-UHFFFAOYSA-N Histamine Chemical compound NCCC1=CN=CN1 NTYJJOPFIAHURM-UHFFFAOYSA-N 0.000 abstract description 10
- 150000003752 zinc compounds Chemical class 0.000 abstract description 9
- VIHYIVKEECZGOU-UHFFFAOYSA-N N-acetylimidazole Chemical compound CC(=O)N1C=CN=C1 VIHYIVKEECZGOU-UHFFFAOYSA-N 0.000 abstract description 7
- 125000002883 imidazolyl group Chemical group 0.000 abstract description 7
- OXFSTTJBVAAALW-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione Chemical compound SC1=NC=CN1 OXFSTTJBVAAALW-UHFFFAOYSA-N 0.000 abstract description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004246 zinc acetate Substances 0.000 abstract description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 abstract description 6
- 229960001763 zinc sulfate Drugs 0.000 abstract description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 abstract description 6
- ZEVWQFWTGHFIDH-UHFFFAOYSA-N 1h-imidazole-4,5-dicarboxylic acid Chemical compound OC(=O)C=1N=CNC=1C(O)=O ZEVWQFWTGHFIDH-UHFFFAOYSA-N 0.000 abstract description 5
- 229960001340 histamine Drugs 0.000 abstract description 5
- QAFBDRSXXHEXGB-UHFFFAOYSA-N imidazol-1-ylacetic acid Chemical compound OC(=O)CN1C=CN=C1 QAFBDRSXXHEXGB-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 150000005846 sugar alcohols Polymers 0.000 abstract description 4
- 150000004677 hydrates Chemical class 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000011347 resin Substances 0.000 description 23
- 229920005989 resin Polymers 0.000 description 23
- 239000000203 mixture Substances 0.000 description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000000227 grinding Methods 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000011592 zinc chloride Substances 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 239000003017 thermal stabilizer Substances 0.000 description 4
- HVCYQHMPRZHRTI-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione;zinc Chemical compound [Zn].S=C1NC=CN1 HVCYQHMPRZHRTI-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- 150000004291 polyenes Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of plastic additives, in particular to a zinc-containing complex, a preparation method thereof and a plastic additive containing the zinc-containing complex. The zinc-containing complex is prepared by in-situ reaction of an imidazole compound and a metallic zinc compound, wherein the zinc-containing complex contains an imidazole group, the imidazole compound is one or more of imidazole, histamine, 2-mercaptoimidazole, 1-acetylimidazole, imidazole-4, 5-dicarboxylic acid and imidazole-1-acetic acid, and the metallic zinc compound is one or one of hydrates of zinc acetate, zinc nitrate and zinc sulfate. The plastic auxiliary agent consists of a zinc-containing complex, an epoxy compound, polyhydric alcohol, beta-diketone and C12-C18 long-chain fatty acid. The zinc-containing complex can be used independently, avoids zinc burning, endows the polyvinyl chloride product with initial whiteness, and has the advantages of simple preparation method and no solvent addition. The components in the plastic additive prepared from the zinc-containing complex are synergistically strengthened, so that the polyvinyl chloride product has stronger thermal stability.
Description
Technical Field
The invention relates to the technical field of plastic additives, in particular to a zinc-containing complex, a preparation method thereof and a plastic additive containing the zinc-containing complex.
Background
Polyvinyl chloride is one of five general-purpose plastics, the yield is second to that of polyethylene, and the product has the advantages of excellent mechanical property, corrosion resistance and chemical resistance, good insulating property, flame retardancy, high transparency and the like, and can be widely applied to the fields of industrial buildings, agriculture, packaging, electronics, textiles, daily necessities, aviation, machinery, transportation, public utilities and the like. However, the polyvinyl chloride resin has poor thermal stability, and the polyvinyl chloride resin starts to degrade at 100 ℃ to release hydrogen chloride gas, and a chromophoric conjugated polyene structure is formed on a molecular chain, so that the application of the polyvinyl chloride resin is limited. For a long time, the additives used for retarding the pyrolysis of polyvinyl chloride mainly include lead salts, metallic soaps, organic tin and rare earths. Since the middle of the 60's of the 20 th century, the use of lead salt-based additives has been limited due to a series of public nuisance problems. At present, the most widely used are organotin and composite calcium/zinc type auxiliaries. The organotin auxiliaries have outstanding stability and transparency, but are expensive, so that their use is greatly restricted, in particular in the field of pipes and profiles. On the other hand, calcium/zinc soaps are inexpensive, but have disadvantages such as unsatisfactory long-term thermal stability, large initial coloring of resins, and poor initial whiteness of polyvinyl chloride products. Meanwhile, the preparation process of the calcium/zinc soap auxiliary agent is complex, a large amount of solvent is needed in the preparation process, and the environmental pollution and the resource waste are easily caused. In addition, an auxiliary agent mainly composed of an organic compound has been developed, and such an auxiliary agent does not contain a metal ion and is becoming a research and development focus. However, the organic auxiliary agents have undesirable effects when used alone, and can generate good synergistic thermal stability effects when used together with other auxiliary agents. Chinese patent CN201210203290.0, entitled multifunctional additive for hard polyvinyl chloride, published as 2012, 6/20, discloses a hard polyvinyl chloride additive prepared from methacrylic acid monomer, butyl acrylate monomer, rare earth stearate, stearic acid, paraffin, calcium carbonate, silica, etc. the additive has the functions of lubricity, processing modification, low-temperature impact resistance, light stability, thermal stability, etc., but the additive is suitable for hard polyvinyl chloride, and the thermal stability effect cannot meet the wide application of polyvinyl chloride thermal processing.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a zinc-containing complex and a plastic additive containing the zinc-containing complex, wherein the zinc-containing complex can be used independently and has a better thermal stability effect on polyvinyl chloride resin. The plastic additive prepared from the zinc-containing complex and an epoxy compound has a long-acting heat stabilization effect on polyvinyl chloride products.
It is another object of the present invention to provide a process for the preparation of the zinc-containing complex. The method is simple and convenient to operate, low in energy consumption, free of solvent and more environment-friendly and economical.
The invention provides the following technical scheme:
the zinc-containing complex is prepared by reacting imidazole compounds with metallic zinc compounds, and contains imidazolyl groups.
As an improvement of the invention, the imidazole compound is one or more of imidazole, histamine, 2-mercaptoimidazole, 1-acetylimidazole, imidazole-4, 5-dicarboxylic acid and imidazole-1-acetic acid.
As an improvement of the invention, the metallic zinc compound is one of zinc acetate, zinc nitrate and zinc sulfate, or one of their respective hydrates.
The zinc-containing complex is prepared by carrying out a complexing reaction on an imidazole compound and a metallic zinc compound. Wherein the imidazole compound is mainly one or more of imidazole, histamine, 2-mercaptoimidazole, 1-acetylimidazole, imidazole-4, 5-dicarboxylic acid and imidazole-1-acetic acid, and the structural formula is as follows.
The imidazolyl group in the imidazole compound can replace unstable chlorine on a polyvinyl chloride resin molecular chain, reduce the formation of conjugated double bonds on the polyvinyl chloride molecular chain, inhibit the thermal degradation of polyvinyl chloride and endow a polyvinyl chloride product with better initial whiteness. And the anionic groups on the metal zinc compound can replace unstable chlorine on the molecular chain of the polyvinyl chloride resin, so that the thermal degradation of the polyvinyl chloride is effectively inhibited. Thus passing throughThe zinc-containing complex prepared by the complex reaction contains zinc ions and imidazolyl groups, and the zinc ions and the imidazolyl groups are mutually reinforced in a synergistic manner, so that the zinc-containing complex has stronger thermal stability to the polyvinyl chloride resin. Compared with the existing organic auxiliary agent, the self chemical stability of the zinc-containing complex is improved, and the zinc-containing complex can be used independently. In addition, the zinc in the calcium/zinc composite auxiliary agent and the chlorine in the polyvinyl chloride resin are easy to form ZnCl2，ZnCl2Can catalyze the degradation of polyvinyl chloride, thereby generating 'zinc burning'. The imidazolyl group in the zinc-containing complex can compete with zinc for chlorine and inhibit ZnCl2The zinc-containing complex can generate certain complexing effect with ZnCl2, thereby effectively inhibiting the generation of 'zinc burning', leading the zinc-containing complex to have better thermal stability to polyvinyl chloride resin and endowing the polyvinyl chloride product with better initial whiteness.
The preparation method of the zinc-containing complex comprises the following steps:
(1) taking the weight percentage of the target zinc-containing complex as 100%, mixing 50-80% of imidazole compound and 20-50% of metallic zinc compound, and then grinding in a ball mill to obtain a mixture;
(2) placing the mixture in a reaction kettle, heating to 160-210 ℃, stirring and reacting for 1-5 hours;
(3) adding water into the reaction kettle after the reaction is finished and refluxing for 2-4 hours;
(4) and cooling to room temperature, carrying out suction filtration and drying, and grinding the obtained product in a ball mill for 1-3 hours to obtain the zinc-containing complex.
In the preparation process of the zinc-containing complex, the imidazole compound and the metallic zinc compound are uniformly mixed, heated to 160-210 ℃ and then subjected to in-situ reaction to prepare the zinc-containing complex. No solvent is needed to be added, the reaction temperature is low, and compared with a calcium/zinc auxiliary agent, the preparation process is simpler, cleaner and environment-friendly.
The plastic additive containing the zinc-containing complex comprises, by weight, 55.0-80.0% of the zinc-containing complex, 5.0-10.0% of an epoxy compound, 2.0-16.0% of a polyol, 6.0-9.0% of a beta-diketone and 7.0-10.0% of a C12-C18 long-chain fatty acid.
As an improvement of the invention, the plastic additive consists of 60.0 to 75.0 percent of zinc-containing complex, 6.0 to 8.0 percent of epoxy compound, 4.0 to 14.0 percent of polyol, 7.0 to 9.0 percent of beta-diketone and 8.0 to 9.0 percent of long-chain fatty acid of C12 to C18.
As an improvement of the invention, the plastic additive consists of 70.0 percent of zinc-containing complex, 7.0 percent of epoxy compound, 7.0 percent of polyol, 8.0 percent of beta-diketone and 8.0 percent of long-chain fatty acid of C12-C18.
As an improvement of the invention, the epoxy compound is epoxidized soybean oil, epoxidized sunflower oil or epoxidized fatty acid methyl ester.
As a refinement of the invention, the polyol is pentaerythritol, dipentaerythritol or sorbitol.
As a modification of the present invention, the beta-diketone is stearoylbenzoylmethane or dibenzoylmethane.
The plastic additive is prepared by mixing a zinc-containing complex, an epoxy compound, a polyol, a beta-diketone and C12-C18 long-chain fatty acid, wherein the epoxy compound has the capacity of absorbing HCl, and when the epoxy compound and the zinc-containing complex are compounded for use, unstable chlorine can be replaced under the catalytic action of metal ions, and the epoxy compound can be added with a conjugated polyene chain segment to inhibit the coloring of a polyvinyl chloride product and reduce the initial coloring capacity of the polyvinyl chloride product. The C12-C18 long-chain fatty acid, the polyalcohol and the beta-diketone have strong complexing ZnCl2The ability of the cell to perform. When the complex is used together with a zinc-containing complex, the complex can effectively complex polyvinyl chloride with a small amount of ZnCl generated by zinc2Thereby enhancing the effect of the imidazolyl group in inhibiting 'zinc burn'. Thus, through reasonable configuration and mutual synergy of the zinc-containing complex, the epoxy compound, the long-chain fatty acid, the polyol, the beta-diketone and the like, the obtained plastic auxiliary agent can inhibit thermal degradation of the polyvinyl chloride resin, inhibit 'zinc burning' phenomenon compared with a calcium/zinc composite auxiliary agent, simultaneously reduce the initial coloring capacity of the polyvinyl chloride resin product, realize long-acting thermal stability of the polyvinyl chloride product, and can be widely applied to various polyvinyl chloride productsHot processing the product and the plastic containing chlorine resin. In addition, the preferable plastic additive is that when the plastic additive is applied to the thermal processing of polyvinyl chloride resin, the mass ratio of the plastic additive to the polyvinyl chloride resin is 3-5: 100.
The invention has the following beneficial effects:
compared with an organic assistant, the zinc-containing complex disclosed by the invention can be used independently, so that the thermal degradation of the polyvinyl chloride resin is inhibited, and compared with a calcium/zinc assistant, the zinc burning can be avoided, so that the initial whiteness of a polyvinyl chloride product is endowed, and the preparation method is simple, free of solvent addition, environment-friendly and economical. Meanwhile, the plastic additive prepared from the zinc-containing complex is synergistically strengthened by all components, so that the long-acting thermal stability of the processing of polyvinyl chloride products can be realized, the initial coloring capacity of the polyvinyl chloride resin products is reduced, and the polyvinyl chloride resin additive can be widely applied to the processing of various polyvinyl chloride products and plastics containing chlorine resin.
Drawings
FIG. 1 is a graph showing the effect of the plastic additives obtained in examples 4 to 6.
FIG. 2 is a graph showing the effects of the plastic additives obtained in examples 7 to 8.
FIG. 3 is a graph showing the effects of the additives obtained in examples 9 to 11.
FIG. 4 is a graph showing the effect of using HCZ1086F calcium-zinc plastic adjuvant in comparison.
Detailed Description
The following further describes the embodiments of the present invention.
The starting materials used in the present invention are commercially available or commonly used in the art, unless otherwise specified, and the methods in the following examples are conventional in the art, unless otherwise specified.
The C12-C18 long-chain fatty acid used in the invention is one of stearic acid or palmitic acid.
1. Zinc-containing complexes and their preparation
Example 1
The zinc-containing complex is a dithioic acid-bis (1-acetylimidazole) zinc complex prepared by the complex reaction of 1-acetylimidazole and zinc sulfate, and is prepared by the following steps:
(1) taking 80% of 1-acetyl imidazole and 20% of zinc sulfate to be mixed according to the weight percentage of 100% of the obtained zinc-containing complex, and then grinding the mixture in a ball mill to obtain a mixture;
(2) placing the mixture in a reaction kettle, heating to 210 ℃, stirring and reacting for 1 hour;
(3) adding water into the reaction kettle after the reaction is finished and refluxing for 2 hours;
(4) cooling to room temperature, carrying out suction filtration and drying, and grinding the obtained product in a ball mill for 1 hour to obtain the zinc-containing complex.
Example 2
A zinc-containing complex is diacetic acid-bis (2-mercaptoimidazole) zinc prepared by the complex reaction of 2-mercaptoimidazole and zinc acetate, and the preparation steps are as follows:
(1) taking 65% of 2-mercaptoimidazole and 35% of zinc acetate to be mixed according to the weight percentage of 100% of the obtained zinc-containing complex, and then grinding the mixture in a ball mill to obtain a mixture;
(2) placing the mixture in a reaction kettle, heating to 180 ℃, stirring and reacting for 3 hours;
(3) adding water into the reaction kettle after the reaction is finished and refluxing for 3 hours;
(4) cooling to room temperature, carrying out suction filtration and drying, and grinding the obtained product in a ball mill for 2 hours to obtain the zinc-containing complex.
Example 3
The zinc-containing complex is zinc dinitrate-diimidazole complex prepared by the complex reaction of imidazole and zinc nitrate, and the preparation steps are as follows:
(1) taking the obtained zinc-containing complex as 100% by weight, mixing 50% of imidazole and 20% of zinc nitrate, and then grinding in a ball mill to obtain a mixture;
(2) placing the mixture in a reaction kettle, heating to 160 ℃, stirring and reacting for 5 hours;
(3) adding water into the reaction kettle after the reaction is finished and refluxing for 4 hours;
(4) cooling to room temperature, carrying out suction filtration and drying, and grinding the obtained product in a ball mill for 3 hours to obtain the zinc-containing complex.
2. Plastic auxiliary agent
Examples 4 to 6
The preparation method comprises the following steps: the zinc dithioate-bis (1-acetylimidazole) obtained in example 1, the polyol, the epoxy compound, the long-chain fatty acid and the beta-diketone are put into a mixer according to the proportion, stirred and mixed for 50min at the speed of 60r/min, and then the mixture is added into a ball mill to be ground for 3 hours to obtain the plastic additive. The composition of the individual plastic auxiliaries is shown in Table 1.
TABLE 1 Plastic auxiliaries containing zinc bis (1-acetylimidazole) disulfate from example 1
| Raw materials | Example 4 | Example 5 | Example 6 |
| Bis (1-acetylimidazole) zinc disulfate | 55g | 70g | 80g |
| Epoxidized soybean oil | 10g | 8g | 5g |
| Dibenzoylmethane | 9g | 8g | 6g |
| Pentaerythritol | 16g | 12g | 2g |
| Stearic acid | 10g | 2g | 7g |
5g of each of the plastic additives prepared in examples 4 to 6 was mixed with 100g of SG-5 polyvinyl chloride resin powder, 15g of calcium carbonate and 8g of lubricant in a high-speed mixer, and then plasticated in a sheet form on a twin-roll mixer with a roll temperature of 180 ℃ and a roll gap of 1mm, and then cut into small sample strips of 30mm × 20mm, the sample strips were placed on an aluminum plate, the aluminum plate was heated in a blowing oven at 180 ℃, and the sample strips were taken out every 10 minutes and used for recording the color change until the sample strips completely turn black, so as to measure the thermal stability of the composite thermal stabilizer, and the results are shown in FIG. 1.
Examples 7 to 8
The preparation method comprises the following steps: the diacetic acid-bis (2-mercaptoimidazole) zinc obtained in example 2, polyhydric alcohol, epoxy compound, long chain fatty acid and beta-diketone are put into a mixer, stirred and mixed for 50min at the speed of 60r/min, and then the mixture is added into a ball mill to be ground for 3 hours to obtain the plastic additive. The composition of the individual plastic auxiliaries is shown in Table 2.
TABLE 2 Plastic auxiliaries containing zinc diacetate-bis (2-mercaptoimidazole) obtained in example 2
| Raw materials | Example 7 | Example 8 |
| Diacetic acid-bis (2-mercaptoimidazole) zinc | 66g | 72g |
| Epoxy sunflower oil | 8g | 7g |
| Stearoylbenzoylmethane | 9g | 7g |
| Bispentaerythritol | 9g | 5g |
| Palmitic acid | 8g | 9g |
4g of each of the plastic additives prepared in examples 7 to 8 was mixed with 100g of a polyvinyl chloride resin powder of SG-5 type, 15g of calcium carbonate and 8g of a lubricant in a high-speed mixer, and then plasticated in a sheet form on a twin-roll mixer with a roll temperature of 180 ℃ and a roll gap of 1mm, and then cut into small sample strips of 30mm × 20mm, the sample strips were placed on an aluminum plate, the aluminum plate was heated in a forced air oven at 180 ℃, and the sample strips were taken out every 10 minutes and used for recording the color change until the sample strips completely turn black, so that the thermal stability of the composite thermal stabilizer was measured, and the results are shown in FIG. 2.
Examples 9 to 11
The preparation method comprises the following steps: and (2) putting the zinc dinitrate-diimidazole obtained in the example 3, polyhydric alcohol, epoxy compound, long-chain fatty acid and beta-diketone into a mixer, stirring and mixing for 50min at the speed of 60r/min, and then adding the mixture into a ball mill for grinding for 3 hours to obtain the plastic additive. The composition of the individual plastic auxiliaries is shown in Table 3.
TABLE 3 Plastic auxiliaries containing zinc dinitrate-diimidazole obtained in example 2
| Raw materials | Example 9 | Example 10 | Example 11 |
| Zinc dinitrate-diimidazole complex | 64g | 70g | 75g |
| Epoxidized fatty acid methyl ester | 8g | 7g | 6g |
| Stearoylbenzoylmethane | 9g | 8g | 7g |
| Sorbitol | 10g | 7g | 4g |
| Stearic acid | 9g | 8g | 8g |
3g of each of the plastic additives prepared in examples 9 to 11 was mixed with 100g of SG-5 polyvinyl chloride resin powder, 15g of calcium carbonate and 8g of lubricant in a high speed mixer, and then plasticated in a sheet form on a twin roll mixer with a roll temperature of 180 ℃ and a roll gap of 1mm, and then cut into small sample strips of 30mm × 20mm, the small sample strips were placed on an aluminum plate, the aluminum plate was heated in a blowing oven at 180 ℃, and the sample strips were taken out every 10 minutes and used for recording the color change until the sample strips completely turn black, so as to measure the thermal stability of the composite thermal stabilizer, and the results are shown in FIG. 3.
Comparative example
The thermal stability of the composite thermal stabilizer was determined by mixing 5g of a commercially available calcium-zinc plastic additive (model HCZ 1086F) produced by Happon materials Co., Ltd., Zhejiang, with 100g of polyvinyl chloride resin powder (model SG-5), 15g of calcium carbonate, and 8g of a lubricant in a high mixing machine, plasticating the mixture into sheets on a double-roll mixing mill with a roll gap of 1mm at a roll temperature of 180 ℃, cutting the sheets into small strips of 30mm × 20mm, placing the strips on an aluminum plate, heating the aluminum plate in a blowing oven at 180 ℃, taking out the strips every 10 minutes, and recording the color change with a scanner until the strips become completely black, with the result shown in FIG. 4.
As can be seen from the comparison between FIGS. 1 to 3 and FIG. 4, under the same experimental conditions, the thermal stability of the polyvinyl chloride product added with the plastic additive of the invention is obviously superior to that of the comparative example, and the thermal degradation time is delayed.
In the above embodiments 1 to 11, but not limited to the above embodiments, the imidazole compound may be selected from histamine, imidazole-4, 5-dicarboxylic acid or imidazole-1-acetic acid, or a mixture of two or more of imidazole, histamine, imidazole-4, 5-dicarboxylic acid, 1-acetylimidazole, imidazole-1-acetic acid and 2-mercaptoimidazole, and the metal zinc compound may be selected from zinc acetate, a water mixture of zinc sulfate and zinc nitrate, or a mixture of two or more of zinc acetate, zinc sulfate and zinc nitrate and a hydrate thereof, and the performance of the obtained plastic additive is substantially maintained.
Claims (6)
1. The plastic additive containing the zinc-containing complex is characterized by being prepared by mixing 55.0-80.0% of the zinc-containing complex, 5.0-10.0% of epoxy compound, 2.0-16.0% of polyol, 6.0-9.0% of beta-diketone and 7.0-10.0% of C12-C18 long-chain fatty acid in percentage by weight;
wherein the zinc-containing complex is one of zinc disulfate-bis (1-acetylimidazole) complex, zinc diacetate-bis (2-mercaptoimidazole) complex and zinc dinitrate-diimidazole complex.
2. The plastic additive as claimed in claim 1, wherein the plastic additive is prepared by mixing 60.0-75.0% of zinc-containing complex, 6.0-8.0% of epoxy compound, 4.0-14.0% of polyol, 7.0-9.0% of beta-diketone and 8.0-9.0% of C12-C18 long-chain fatty acid.
3. The plastic additive as claimed in claim 1, wherein the plastic additive is prepared by mixing 70.0% of zinc-containing complex, 7.0% of epoxy compound, 7.0% of polyol, 8.0% of beta-diketone and 8.0% of long-chain fatty acid C12-C18.
4. A plastic adjuvant according to any one of claims 1 to 3, characterized in that the epoxy compound is epoxidized soybean oil, epoxidized sunflower oil or epoxidized fatty acid methyl ester.
5. A plastic adjuvant according to any of claims 1 to 3, characterized in that the polyol is pentaerythritol, dipentaerythritol or sorbitol.
6. A plastics additive according to any one of claims 1 to 3, wherein the β -diketone is stearoylbenzoylmethane or dibenzoylmethane.
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