CN103524945B - Technology for preparing efficient environment-friendly compound heat stabilizer for polyvinyl chloride hard products - Google Patents
Technology for preparing efficient environment-friendly compound heat stabilizer for polyvinyl chloride hard products Download PDFInfo
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- CN103524945B CN103524945B CN201310480966.5A CN201310480966A CN103524945B CN 103524945 B CN103524945 B CN 103524945B CN 201310480966 A CN201310480966 A CN 201310480966A CN 103524945 B CN103524945 B CN 103524945B
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- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 39
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 39
- 238000005516 engineering process Methods 0.000 title claims abstract description 30
- 150000001875 compounds Chemical class 0.000 title claims abstract description 22
- 239000012760 heat stabilizer Substances 0.000 title abstract description 9
- 239000004593 Epoxy Substances 0.000 claims abstract description 27
- -1 ketone compounds Chemical class 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000000314 lubricant Substances 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 17
- 239000000194 fatty acid Substances 0.000 claims abstract description 17
- 229930195729 fatty acid Natural products 0.000 claims abstract description 17
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 10
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 10
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000004898 kneading Methods 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims description 35
- 239000003017 thermal stabilizer Substances 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 23
- 239000011575 calcium Substances 0.000 claims description 19
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 18
- 229910052791 calcium Inorganic materials 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 235000019441 ethanol Nutrition 0.000 claims description 17
- 239000003112 inhibitor Substances 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 238000009775 high-speed stirring Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 235000021355 Stearic acid Nutrition 0.000 claims description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 10
- 239000008117 stearic acid Substances 0.000 claims description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 8
- 229940059574 pentaerithrityl Drugs 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 7
- 239000000920 calcium hydroxide Substances 0.000 claims description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 7
- 150000002632 lipids Chemical class 0.000 claims description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 230000001404 mediated effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 5
- 239000004386 Erythritol Substances 0.000 claims description 4
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 4
- 239000005639 Lauric acid Substances 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 239000004359 castor oil Substances 0.000 claims description 4
- 235000019438 castor oil Nutrition 0.000 claims description 4
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 4
- 235000019414 erythritol Nutrition 0.000 claims description 4
- 229940009714 erythritol Drugs 0.000 claims description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 3
- PCHSZUARHVFVED-UHFFFAOYSA-N C(=O)C.C1(=CC=CC=C1)C(=O)CC(C)C Chemical compound C(=O)C.C1(=CC=CC=C1)C(=O)CC(C)C PCHSZUARHVFVED-UHFFFAOYSA-N 0.000 claims description 3
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 claims description 3
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical group 0.000 claims description 3
- 125000005594 diketone group Chemical group 0.000 claims description 3
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- 239000000811 xylitol Substances 0.000 claims description 3
- 235000010447 xylitol Nutrition 0.000 claims description 3
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 3
- 229960002675 xylitol Drugs 0.000 claims description 3
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 3
- 229940007718 zinc hydroxide Drugs 0.000 claims description 3
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims 2
- FEXXLIKDYGCVGJ-UHFFFAOYSA-N butyl 8-(3-octyloxiran-2-yl)octanoate Chemical compound CCCCCCCCC1OC1CCCCCCCC(=O)OCCCC FEXXLIKDYGCVGJ-UHFFFAOYSA-N 0.000 claims 1
- 229940075507 glyceryl monostearate Drugs 0.000 claims 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 claims 1
- 229940056211 paraffin Drugs 0.000 claims 1
- 239000003963 antioxidant agent Substances 0.000 abstract description 2
- 230000003078 antioxidant effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract 2
- 238000003756 stirring Methods 0.000 abstract 2
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 abstract 1
- 229940043430 calcium compound Drugs 0.000 abstract 1
- 150000001674 calcium compounds Chemical class 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 238000003754 machining Methods 0.000 abstract 1
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- 150000003752 zinc compounds Chemical class 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 19
- 229910052725 zinc Inorganic materials 0.000 description 19
- 230000007613 environmental effect Effects 0.000 description 14
- 239000003381 stabilizer Substances 0.000 description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- 230000018109 developmental process Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229910052712 strontium Inorganic materials 0.000 description 7
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 125000005456 glyceride group Chemical group 0.000 description 3
- IMYZYCNQZDBZBQ-UHFFFAOYSA-N (+-)-8-(cis-3-octyl-oxiranyl)-octanoic acid Natural products CCCCCCCCC1OC1CCCCCCCC(O)=O IMYZYCNQZDBZBQ-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- AWDJLJNCSGUBSK-UHFFFAOYSA-N [Ca].CC(C)=O Chemical compound [Ca].CC(C)=O AWDJLJNCSGUBSK-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- BAOGIWGDRNSXGA-UHFFFAOYSA-N propan-2-one;zinc Chemical compound [Zn].CC(C)=O BAOGIWGDRNSXGA-UHFFFAOYSA-N 0.000 description 2
- 150000003437 strontium Chemical class 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 239000004605 External Lubricant Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 150000004291 polyenes Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Abstract
The invention relates to a technology for preparing an efficient environment-friendly compound heat stabilizer for polyvinyl chloride hard products. The technology comprises the steps of putting fatty acid into a reaction kettle with a stirrer, a thermometer and a condenser, sequentially adding calcium compounds and zinc compounds, and obtaining liquid fatty acid metal salt; preparing into solid sheets through molding equipment, then grinding, and adding an antioxidant, a lubricant, polyhydric alcohols, ketone compounds and hydrotalcite into a high speed kneading machine; and stirring at high speed and carrying out kneading reaction, then adding epoxy compounds, stirring, and preparing the final product. The technology is mainly used for machining polyvinyl chloride environment-friendly hard products, can improve the heat stability of traditional calcium-zinc compound heat stabilizers, and substitutes lead and salt heat stabilizers.
Description
Technical field
The present invention relates to fine chemical technology field, the specifically preparation technology of high-efficiency environment friendly composite thermal stabilizer for a kind of polyvinyl chloride boardy product, is mainly used in the processing of polyvinyl chloride environmental protection boardy product.
Background technology
Polyvinyl chloride (PVC) is the large general-purpose plastics in third place in the world, is only second to polyethylene (PE) and polypropylene (PP).It has cheap, corrosion-resistant, ageing-resistant, the transparency is good, mechanical property is excellent, electrical insulating property good and the advantage such as fire-retardant, its goods are widely used in the industries such as building, chemical industry, electrical equipment.Due to the labile factor of polyvinyl chloride (PVC) RESINS molecular structure existence, be heated and the effect of oxygen under very easily decompose, lose use value, therefore in the polyvinyl chloride course of processing, must add thermo-stabilizer, prevent that it is because being subject to high temperature and mechanical shear stress is degraded.
China is that polychloroethylene heat stabilizer is produced consumption big country but not manufacture power, and lead salt stabilizer is occupied an leading position for a long time in China's stablizer market.Along with the enhancing of domestic and international environmental consciousness, in succession put into effect a series of environmental regulation, as WWWE instruction and ROHS instruction, limited or forbid the use of heavy metal in thermo-stabilizer, lead salt stabilizer will progressively be eliminated, and environmentfriendly products become future developing trend.Environmental Protection in China thermo-stabilizer state of the art still has one section of gap compared with same kind of products at abroad, and performance need to improve, and the high-efficiency environment friendly thermo-stabilizer that polyvinyl chloride boardy product is used at present relies on import substantially.And the fast development of China's PVC industry, the great attention of government to environmental protection, for thermo-stabilizer provides the good market space without poisoning fast development, also has higher requirement to thermo-stabilizer industry simultaneously.Along with increasing achievement in research is to industrial conversion, greatly advance thermo-stabilizer high-performance without poisoning process, dwindle gradually with world-class gap.
Because the level of economic development of China is also lower, polyvinyl chloride processing industry dog-eat-dog, is difficult to accept the price of organic tin thermo-stabilizer costliness, so cheap and good-quality Ca Zn composite series products is that China's thermo-stabilizer is without the first-selected approach that poisons development.Along with the development of industry technology, multifunctional high-performance complex class product, high performance-price ratio, potion multipotency have become the development trend of polychloroethylene heat stabilizer, and safety and environmental protection, energy-saving and emission-reduction become development priority, multifunctional high-performance complex class, specification refinement become research and development focus.By the function of multiple auxiliary agent being attached to it one " comprehensive auxiliary agent ", or multiple auxiliary agent is broken into one " superpacket " with suitable proportioning, auxiliary agent has just been realized and has been comprised that stability, antioxidant, light fastness aging, processibility, enhancement etc. are in the over-all properties of one, very convenient to use, be kind most popular on market, abroad Ge great auxiliary agent company goes after in a swarm to this.
Existing environmental protection composite thermal stabilizer ubiquity poor heat stability, the problem that cost is high.Often postpone plasticizing by adding external lubricant, improve processing characteristics and meet polyvinyl chloride boardy product production requirement.Therefore cause polyvinyl chloride boardy product plasticizing poor, intensity is low, and physicals is poor, is not durable.As need reach the performance requriements containing lead stabilizer, need to improve usage quantity, or add expensive auxiliary agent and realize, manufacturing cost increases considerably, a little less than the market competitiveness.The present invention utilizes the Symbiont of innovative technology synthetic fatty acid calcium, zinc, be aided with novel inorganic and organic auxiliary stabilizer carries out composite, prepare a kind of novel environment friendly composite thermal stabilizer, solve the general poor heat stability of current domestic PVC boardy product environmental protection composite thermal stabilizer, addition is large, the higher and poor difficult problem of goods physicals of cost.The composite thermal stabilizer formulating of recipe theory of abandoning tradition of the present invention, adopt full effect formulating of recipe thinking, by introducing mathematics orthogonal test pattern, utilize drug matching principle, rational allocation, give full play to the synergy of each component, between stability and processibility, find optimum point, adopt the production technique of short flow process to prepare efficient full effect, multi-functional polyvinyl chloride environmental protection composite thermal stabilizer.
Summary of the invention
The object of the invention is in order to improve traditional Ca-Zn composite heat stabilizer thermal stability, replace lead salts thermo-stabilizer and the preparation technology of a kind of polyvinyl chloride boardy product high-efficiency environment friendly composite thermal stabilizer that provides.
In order to achieve the above object, the designed a kind of polyvinyl chloride boardy product of the present invention preparation technology of high-efficiency environment friendly composite thermal stabilizer is the mixture of fatty acids metal-salt, oxidation inhibitor, lubricant, polyvalent alcohol, ketone compounds, epoxy compounds and hydrotalcite;
The preparation technology of polyvinyl chloride environmental protection composite thermal stabilizer:
The first step drops into lipid acid in the reactor that agitator, thermometer and condenser are housed, and adds successively calcium cpd, zn cpds; The mol ratio ratio feeding intake is: lipid acid: zn cpds: calcium cpd=4.4～11.0: 1.8～4.2: 0.4～1.3; At 90～140 DEG C of temperature, react, now have water vapour to produce, in the time that the anhydrous drip of condensator outlet goes out, then holding temperature to 120～160 DEG C reaction 2 hours, finish reaction and obtaining liquid aliphatic acid metal salt;
Second step, by there being the molding device of refrigerating unit to make solid sheet, then becomes fineness 200 object fatty acid metal salt powders by solid sheet crushing material with high speed disintegrator by liquid aliphatic acid metal salt;
The 3rd step drops into successively by mass percentage fatty acid metal salt powder 14～42%, oxidation inhibitor 1.5～7.5%, lubricant 9～40%, polyvalent alcohol 2.5～10%, ketone compounds 0.5～8.5% and hydrotalcite 5～32% in high-speed kneading machine; High-speed stirring is mediated, and reacts 5～10 minutes, and temperature rises to 40～70 DEG C, makes homogeneous powder product;
The 4th step, maintains 40～70 DEG C of temperature of reaction, and the liquid epoxy compound of mass percent 2.5～10.5% is added in homogeneous powder product, and high-speed stirring 2～5 minutes, makes wettability powdery the finished product.
Described lipid acid is lauric acid, stearic acid or palmitinic acid.
Described zn cpds is zinc oxide or zinc hydroxide.
Described calcium cpd is calcium oxide or calcium hydroxide.
Described oxidation inhibitor is amine, Hinered phenols or phosphorous acid esters.
Described lubricant comprises it being PE wax, paraffin, stearic acid list glyceride or pentaerythritol resin.
Described polyvalent alcohol is tetramethylolmethane, sorbyl alcohol, Xylitol or erythritol.
Described ketone compounds is β～diketone, diphenylpropane-1,3-dione(DPPO), isobutyl phenyl ketone formyl methane, decoyl benzoyl methane, acetone zinc or acetone calcium.
Described epoxy compounds is epoxy soybean oil, epoxy castor oil, epoxystearic acid fourth fat or pungent fat.
The polyvinyl chloride composite heat stabilizer that the present invention obtains and preparation technology thereof, adopt the one step preparation of direct reaction method to there is the fatty acid calcium of molecular structure, the Symbiont of zinc, therefore possess well intramolecular synergy certainly, performance is better than fatty acid calcium, the zinc blend that simple physical is mixed.The each components such as the Symbiont of fatty acid calcium, zinc and oxidation inhibitor, lubricant, polyvalent alcohol, ketone compounds, epoxy compounds and hydrotalcite are mixed under middle temperature to the stable performance loss of avoiding conventional high-temperature hot melt production technique to cause by high-speed stirring.Formula adds people's oily epoxy compounds, and product is made to wettability powdery, has in use avoided airborne dust, has protected user's health.This product is through polynary compound, therefore possessed displacement chlorallylene, absorbing hydrogen chloride, neutralization and passivation Lewis acid, stoping the growth of unsaturated double-bond and suppress formation multi-functional of the conjugated polyene structure that can cause variable color, is a kind of full effect high-efficiency environment friendly composite thermal stabilizer.
The polyvinyl chloride environmental protection composite thermal stabilizer that the present invention obtains, well intramolecular from synergy characteristic because having, the application of the polyvinyl chloride boardy product processing that very applicable high temperature and high speed requires; Be a kind of polyvinyl chloride fatty acid calcium Zn composite heat stabilizer of novel texture, each component, in performance self-acting, can also increase and have synergy component usefulness; To preventing that thermooxidizing from decomposing, improve color and luster etc. and there is outstanding effect.Because it has very high thermostability, oilness, weathering resistance and oxidation-resistance, over-all properties is outstanding, therefore can suitably reduce the addition of other processing aid, be that one does not contain heavy metal ion, meet the new and effective full effect environmental protection composite thermal stabilizer of international and domestic every environmental regulation requirement completely.
Embodiment
The present invention is further described by the following embodiment.
Embodiment 1
A kind of polyvinyl chloride boardy product is being equipped with in the reactor of agitator, thermometer and condenser by the preparation technology of high-efficiency environment friendly composite thermal stabilizer.The first step: drop into the stearic acid of 4.4 moles, temperature drops into the calcium hydroxide of 0.4 mole and reacts at 90～110 DEG C, now has water vapor to produce; Continue rising temperature to 120～140 DEG C and drop into the zinc oxide of 1.8 moles, add 0.01 mole of clear water to carry out catalyzed reaction simultaneously, now have a large amount of water vapors to produce, in the time that water vapor diminishes, 130～150 DEG C of reactions of holding temperature two hours; Finishing reaction makes containing calcium stearate, zinc symbiosis product liquid.Second step, by there being the molding device of refrigerating unit to make solid sheet, becomes 200 object powders by pulverizer by crushing material by aqueous resultant of reaction.The 3rd step drops into successively by mass percentage fatty acid metal salt powder 14%, oxidation inhibitor 1.5%, lubricant 40%, polyvalent alcohol 2.5%, ketone compounds 0.5% and hydrotalcite 31% in high-speed kneading machine; High-speed stirring is mediated, and reacts 5～10 minutes, and temperature rises to 40～70 DEG C, makes homogeneous powder product; The 4th step, maintains 40～70 DEG C of temperature of reaction, and the liquid epoxy compound of mass percent 10.5% is added in homogeneous powder product, and high-speed stirring 2～5 minutes, makes wettability powdery the finished product.
Oxidation inhibitor described in this embodiment is amine, as methane amide; Described lubricant comprises it being PE wax; Described polyvalent alcohol is tetramethylolmethane; Described ketone compounds is β～diketone; Described epoxy compounds is epoxy soybean oil.
Embodiment 2
A kind of polyvinyl chloride boardy product is being equipped with in the reactor of agitator, thermometer and condenser by the preparation technology of high-efficiency environment friendly composite thermal stabilizer.The first step replaces stearic acid by lauric acid; Replace calcium hydroxide with calcium oxide; Operation is undertaken by embodiment 1 the first step; Second step, by there being the molding device of refrigerating unit to make solid sheet, becomes 200 object powders by pulverizer by crushing material by aqueous resultant of reaction.The 3rd step drops into successively by mass percentage fatty acid metal salt powder 40%, oxidation inhibitor 7.5%, lubricant 9%, polyvalent alcohol 10%, ketone compounds 8.5% and hydrotalcite 22.5% in high-speed kneading machine; High-speed stirring is mediated, and reacts 5～10 minutes, and temperature rises to 40～70 DEG C, makes homogeneous powder product; The 4th step, maintains 40～70 DEG C of temperature of reaction, and the liquid epoxy compound of mass percent 2.5% is added in homogeneous powder product, and high-speed stirring 2～5 minutes, makes wettability powdery the finished product.
Oxidation inhibitor described in this embodiment is hindered phenol such as CHEMNOX 1010; Described lubricant is paraffin; Described polyvalent alcohol is sorbyl alcohol; Described ketone compounds is diphenylpropane-1,3-dione(DPPO); Described epoxy compounds is epoxy castor oil.
Embodiment 3
A kind of polyvinyl chloride boardy product is being equipped with in the reactor of agitator, thermometer and condenser by the preparation technology of high-efficiency environment friendly composite thermal stabilizer.The first step replaces stearic acid with palmitinic acid; Replace calcium hydroxide with calcium oxide; Operation is undertaken by embodiment 1 the first step; Second step, by there being the molding device of refrigerating unit to make solid sheet, becomes 200 object powders by pulverizer by crushing material by aqueous resultant of reaction.The 3rd step drops into successively by mass percentage fatty acid metal salt powder 42%, oxidation inhibitor 4%, lubricant 33%, polyvalent alcohol 6.5%, ketone compounds 6% and hydrotalcite 5% in high-speed kneading machine; High-speed stirring is mediated, and reacts 5～10 minutes, and temperature rises to 40～70 DEG C, makes homogeneous powder product; The 4th step, maintains 40～70 DEG C of temperature of reaction, and the liquid epoxy compound of mass percent 3.5% is added in homogeneous powder product, and high-speed stirring 2～5 minutes, makes wettability powdery the finished product.
Oxidation inhibitor described in this embodiment is phosphorous acid esters; Such as: the different fork bis-phenol of phosphorous acid 4,4～bis-(12～14) carbon alkyl ester; Described lubricant is stearic acid list glyceride; Described polyvalent alcohol is Xylitol; Described ketone compounds is isobutyl phenyl ketone formyl methane; Described epoxy compounds is epoxystearic acid fourth fat.
Embodiment 4
Polyvinyl chloride boardy product is to replace a zinc oxide with the zinc hydroxide of 1 mole by the preparation technology of high-efficiency environment friendly composite thermal stabilizer, and operation is undertaken by embodiment 1, produces 1 product with embodiment.Oxidation inhibitor described in this embodiment is CHEMNOX 1010; Described lubricant is pentaerythritol resin; Described polyvalent alcohol is erythritol; Described ketone compounds is decoyl benzoyl methane; Described epoxy compounds is pungent fat.
Embodiment 5
Polyvinyl chloride boardy product is to replace a calcium hydroxide with the calcium oxide of 1 mole by the preparation technology of high-efficiency environment friendly composite thermal stabilizer, and operation is undertaken by embodiment 1, produces 1 product with embodiment.
Described lipid acid is lauric acid, stearic acid or palmitinic acid.
Oxidation inhibitor described in this embodiment is CHEMNOX 1010; Described lubricant is pentaerythritol resin; Described polyvalent alcohol is erythritol; Described ketone compounds is acetone zinc.Described epoxy compounds is epoxy soybean oil.
Embodiment 6
A kind of polyvinyl chloride boardy product is being equipped with in the reactor of agitator, thermometer and condenser by the preparation technology of high-efficiency environment friendly composite thermal stabilizer.The first step replaces stearic acid with palmitinic acid; Replace calcium hydroxide with calcium oxide; Operation is undertaken by embodiment 1 the first step; Second step, by there being the molding device of refrigerating unit to make solid sheet, becomes 200 object powders by pulverizer by crushing material by aqueous resultant of reaction.The 3rd step drops into successively by mass percentage fatty acid metal salt powder 20%, oxidation inhibitor 6.5%, lubricant 15.5%, polyvalent alcohol 9%, ketone compounds 7% and hydrotalcite 32% in high-speed kneading machine; High-speed stirring is mediated, and reacts 5～10 minutes, and temperature rises to 40～70 DEG C, makes homogeneous powder product; The 4th step, maintains 40～70 DEG C of temperature of reaction, and the liquid epoxy compound of mass percent 10% is added in homogeneous powder product, and high-speed stirring 2～5 minutes, makes wettability powdery the finished product.
Oxidation inhibitor described in this embodiment is phosphorous acid esters; Such as: the different fork bis-phenol of phosphorous acid 4,4～bis-(12～14) carbon alkyl ester; Described lubricant comprises it being stearic acid list glyceride; Described polyvalent alcohol is tetramethylolmethane; Described ketone compounds is acetone calcium; Described epoxy compounds is epoxy castor oil.
In addition; because polyvinyl chloride environmental protection composite thermal stabilizer has the various salts such as calcium/zinc, strontium/zinc, magnesium/zinc, calcium/zinc/strontium, calcium/zinc/magnesium, strontium/zinc/magnesium; the operational path of producing is identical; the method that this patent relates to is applicable to strontium/zinc, magnesium/zinc, calcium/zinc/strontium, calcium/zinc/magnesium, strontium/zinc/magnesium salts product of these series product equally, so the products such as the strontium/zinc of these series product, magnesium/zinc, calcium/zinc/strontium, calcium/zinc/magnesium, strontium/zinc/magnesium salts and synthesis technique thereof all belong to the protection domain of this patent.
Claims (9)
1. a preparation technology for high-efficiency environment friendly composite thermal stabilizer for polyvinyl chloride boardy product, described high-efficiency environment friendly composite thermal stabilizer is the mixture of fatty acids metal-salt, oxidation inhibitor, lubricant, polyvalent alcohol, ketone compounds, epoxy compounds and hydrotalcite; It is characterized in that preparation technology is:
The first step drops into lipid acid in the reactor that agitator, thermometer and condenser are housed, and adds successively calcium cpd, zn cpds; The mol ratio ratio feeding intake is: lipid acid: zn cpds: calcium cpd=4.4～11.0: 1.8～4.2: 0.4～1.3; At 90～140 DEG C of temperature, react, now have water vapour to produce, in the time that the anhydrous drip of condensator outlet goes out, then holding temperature to 120～160 DEG C reaction 2 hours, finish reaction and obtaining liquid aliphatic acid metal salt;
Second step, by there being the molding device of refrigerating unit to make solid sheet, then becomes fineness 200 object fatty acid metal salt powders by solid sheet crushing material with high speed disintegrator by liquid aliphatic acid metal salt;
The 3rd step drops into successively by mass percentage fatty acid metal salt powder 14～42%, oxidation inhibitor 1.5～7.5%, lubricant 9～40%, polyvalent alcohol 2.5～10%, ketone compounds 0.5～8.5% and hydrotalcite 5～32% in high-speed kneading machine; High-speed stirring is mediated, and reacts 5～10 minutes, and temperature rises to 40～70 DEG C, makes homogeneous powder product;
The 4th step, maintains 40～70 DEG C of temperature of reaction, and the liquid epoxy compound of mass percent 2.5～10.5% is added in homogeneous powder product, and high-speed stirring 2～5 minutes, makes wettability powdery the finished product.
2. the preparation technology of high-efficiency environment friendly composite thermal stabilizer for a kind of polyvinyl chloride boardy product according to claim 1, is characterized in that, described lipid acid is lauric acid, stearic acid or palmitinic acid.
3. the preparation technology of high-efficiency environment friendly composite thermal stabilizer for a kind of polyvinyl chloride boardy product according to claim 1, is characterized in that, described zn cpds is zinc oxide or zinc hydroxide.
4. the preparation technology of high-efficiency environment friendly composite thermal stabilizer for a kind of polyvinyl chloride boardy product according to claim 1, is characterized in that, described calcium cpd is calcium oxide or calcium hydroxide.
5. the preparation technology of high-efficiency environment friendly composite thermal stabilizer for a kind of polyvinyl chloride boardy product according to claim 1, is characterized in that, described oxidation inhibitor is amine, Hinered phenols or phosphorous acid esters.
6. the preparation technology of high-efficiency environment friendly composite thermal stabilizer for a kind of polyvinyl chloride boardy product according to claim 1, is characterized in that, described lubricant is PE wax, paraffin, glyceryl monostearate or pentaerythritol ester.
7. the preparation technology of high-efficiency environment friendly composite thermal stabilizer for a kind of polyvinyl chloride boardy product according to claim 1, is characterized in that, described polyvalent alcohol is tetramethylolmethane, sorbyl alcohol, Xylitol or erythritol.
8. the preparation technology of high-efficiency environment friendly composite thermal stabilizer for a kind of polyvinyl chloride boardy product according to claim 1, is characterized in that, described ketone compounds is β～diketone, diphenylpropane-1,3-dione(DPPO) or isobutyl phenyl ketone formyl methane.
9. the preparation technology of high-efficiency environment friendly composite thermal stabilizer for a kind of polyvinyl chloride boardy product according to claim 1, is characterized in that, described epoxy compounds is epoxy soybean oil, epoxy castor oil or butyl epoxy stearate.
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| CN105199141A (en) * | 2015-09-15 | 2015-12-30 | 广州盈塑新材料科技有限公司 | One-step novel environment-friendly high-transparency flaky calcium-zinc heat stabilizer and preparation method thereof |
| CN108484981A (en) * | 2018-02-13 | 2018-09-04 | 浙江工业大学 | A kind of long-acting plastic processing additives for delaying thermal degradation and its application |
| CN113980403A (en) * | 2021-09-29 | 2022-01-28 | 湖北金牛管业有限公司 | Injection molding grade PVC-ABS alloy flame-retardant plastic particle and preparation method thereof |
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