CN102477196B - Novel molecular sieve PVC composite stabilizing agent and its preparation method - Google Patents
Novel molecular sieve PVC composite stabilizing agent and its preparation method Download PDFInfo
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- CN102477196B CN102477196B CN201010565585.3A CN201010565585A CN102477196B CN 102477196 B CN102477196 B CN 102477196B CN 201010565585 A CN201010565585 A CN 201010565585A CN 102477196 B CN102477196 B CN 102477196B
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 37
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000003381 stabilizer Substances 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000314 lubricant Substances 0.000 claims abstract description 9
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims abstract description 7
- 235000013539 calcium stearate Nutrition 0.000 claims abstract description 7
- 239000008116 calcium stearate Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 11
- 239000003607 modifier Substances 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000012760 heat stabilizer Substances 0.000 claims description 6
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 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
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 21
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 21
- 229920003023 plastic Polymers 0.000 abstract description 7
- 239000004033 plastic Substances 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract 2
- 230000004048 modification Effects 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000003017 thermal stabilizer Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- 206010047289 Ventricular extrasystoles Diseases 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Abstract
The invention relates to a novel molecular sieve PVC (polyvinyl chloride) composite stabilizing agent and its preparation method. The stabilizing agent is characterized by comprising the following raw materials by mass percent: 20-40% of calcium stearate; 15-25% of zinc stearate; 5-15% of a molecular sieve; 8-20% of a lubricating agent; 8-15% of a surface modification agent; and 5-15% of an auxiliary heat stabilizing agent. The preparation method has no pollution and low energy consumption. According to the national standard GB2113-82 ''test for whiteness of plastics'', the prepared novel modification composite stabilizing agent, compared with traditional stabilizing agents, has excellent thermal stability. And the prepared molecular sieve in the invention has a micropore structure, and diameters of the pores are uniform in size.
Description
Technical field
The invention belongs to PVC manufacture field, particularly a kind of novel molecular sieve PVC one package stabilizer and preparation method thereof.
Background technology
As everyone knows, PVC, under processing temperature condition, easily decomposes, and must add stablizer just can make it process smoothly.In addition, when polyvinyl chloride is heated or is subject to ultraviolet radiation, also can cause degraded and the de-HCl of polymkeric substance.Therefore, PVC's uses and processes and must use stablizer.Stablizer is a kind of chemical assistant, and it can suppress degraded and the variable color that PVC causes due to heat, light action in machine-shaping and use procedure.Stablizer can be divided into base lead salt stablizer, metal soap, organo-tin compound, organic stabilizer and the large class of one package stabilizer five by its chemical structure.
Due to advantages such as lead salt stabilizer raw material are easy to get, production technique is simple, cheap, performance is outstanding, be still so far most widely used kind, output accounts for 65% of China's stablizer output.The shortcoming of lead salt stabilizer is that toxicity is high, coloring plastic is difficult, the bad dispersibility in plastics etc., and particularly powdery lead compound produces a large amount of lead salt dust in batching, stirring or plasticizing process, can produce greatly harm to operator and environment.In order to overcome these shortcomings, mostly adopt complex lead salt stabilizer.Complex lead salt stabilizer is compared with traditional three salt, disalt, and performance improves a lot, and it with strong points, simple to operate reduced the processing technique that is mixed, thereby reduced dust pollution, reduced cost.In a word, complex lead salt stabilizer is famous with its excellent combination property.The complex lead salt stabilizer part that also comes with some shortcomings, as bad dispersibility, poor with PVC base-material consistency, in the finished product of being everlasting, produce white point, have a strong impact on section quality.The problems such as complex lead salt stabilizer also exists painted ability, and versatility is not high.
Molecular sieve is a kind of silico-aluminate compound with cubic(al)grating.Molecular sieve has uniform microvoid structure, its hole diameter is even, the molecular adsorption less than its diameter can be arrived the inside of vestibule in these holes, and polar molecule and saturated molecule are had to preferential adsorptive power, thereby can polarity degree is different, degree of saturation is different, and the different molecular separation of molecular size difference and boiling point comes, there is the effect of " screening " molecule, therefore claim molecular sieve.Due to molecular sieve, to have adsorptive power high, and thermostability waits by force the unexistent advantage of other sorbent material, makes molecular sieve obtain application widely.Molecular sieve is Powdered crystal, has metalluster, and hardness is 3～5, and relative density is 2～2.8, and natural zeolite has color, and synthetic zeolite is white, and water insoluble, thermostability and acid resistance improve along with the increase of SiO2/Al2O3 ratio of components.Molecular sieve has very large specific surface area, reaches 300～1000m2/g, and interior brilliant surface elevation polarization, is a class high-efficiency adsorbent, is also a class solid acid, and there are very high acid concentration and strength of acid in surface, can cause the catalyzed reaction of carbonium ion type.When in the metal ion in forming and solution, other ions exchange, adjustable aperture, changes its adsorption property and catalytic property, thereby makes the molecular sieve catalyst of different performance.
Summary of the invention
Not enough according to prior art, technical problem to be solved by this invention is: a kind of novel molecular sieve PVC one package stabilizer is provided, has the thermostability that adsorptivity is strong and outstanding.
The technical solution adopted for the present invention to solve the technical problems is: a kind of novel molecular sieve PVC one package stabilizer is provided, it is characterized in that being comprised of the raw material of following mass percent:
Calcium stearate 20～40%;
Zinic stearas 15～25%;
Molecular sieve 5～15%;
Lubricant 8～20%;
Surface modifier 8～15%;
Auxiliary heat stabilizer 5～15%.
Described lubricant is polyethylene wax, Tegin 55G or stearic acid.
Described surface modifier is pentaerythritol ester or triphenyl phosphite.
Described auxiliary heat stabilizer is epoxy soybean oil or diphenylpropane-1,3-dione(DPPO).
Described molecular sieve makes in accordance with the following steps:
(1) by kaolin roasting 2～3h at 550～650 ℃;
(2) mix with soda ash, make the component mol ratio in solution be controlled at n (H
2o)/n (Na
2o)/n (SiO
2)=1: 1.5: 2.5, then ageing 2h at 60 ℃;
(3) crystallization 4h under 90 ℃ of hydrothermal conditions;
(4) finally by filtering separation, and to neutrality, be drying to obtain molecular sieve with deionized water wash.
The preparation method of described novel molecular sieve PVC one package stabilizer, it is characterized in that first calcium stearate, Zinic stearas and lubricant being added in reactor and fully being mixed, get mixture, add and in kneader, heat and stir, add surface modifier, at 100～110 ℃, mediate 20min, then in kneader, add composite thermal stabilizer to mediate stirring 30min, discharging compressing tablet, screening mix composite afterwards with molecular sieve, packing.
The present invention adopts composite method, calcium stearate, Zinic stearas are mixed, then add lubricant, surface modifier and auxiliary stabilizer and make stable composition system, then with the composite novel molecular sieve PVC one package stabilizer of making of molecular sieve.
The invention has the beneficial effects as follows: (1) preparation method is pollution-free, energy consumption is low; By GB GB2113-82 " plastics whiteness experimental technique ", from embodiment table 3, can find, prepared new modified one package stabilizer is compared with traditional stablizer, has outstanding thermostability.
(2) the prepared molecular sieve of the present invention, microvoid structure, its hole diameter is even, the molecular adsorption less than its diameter can be arrived the inside of vestibule in these holes, stablizer as plastic workings such as PVC, HCL molecular adsorption can be arrived to the cavity inside of molecular sieve, thereby reach stable effect.Molecular sieve prepared by interpolation the present invention can reduce the consumption of stablizer, reduces costs.By carrying out static-aging experiment to adding the PVC of molecular sieve, result shows, adds the thermostability that one package stabilizer of the present invention can obviously improve PVC.Under 180 ± 1 ℃ of conditions, PVC not only has good initial coloring, and more than its heat-stable time also reached 120～200min.
Embodiment
According to embodiment, the invention will be further described below.
Embodiment 1
(1) by kaolin roasting 2～3h at 550～650 ℃;
(2) mix with soda ash, make the component mol ratio in solution be controlled at n (H
2o)/n (Na
2o)/n (SiO
2)=1: 1.5: 2.5, then ageing 2h at 60 ℃;
(3) crystallization 4h under 90 ℃ of hydrothermal conditions;
(4) finally by filtering separation, and to neutrality, be drying to obtain synthetic product with deionized water wash.
The calcium stearate of preparation, Zinic stearas, lubricant, surface modifier and auxiliary heat stabilizer mix, more composite with molecular sieve, and concrete hybrid mode is as follows:
First 25 parts of 30 parts of calcium stearates, Zinic stearas are added to fully mixing in reactor.Get mixture, add and in kneader, heat and stir, add 15 parts of pentaerythritol esters, at 100～110 ℃, mediate 20min, then in kneader, add 10 parts of polyethylene waxs, 15 parts of epoxy soybean oils, mediate to stir 30min, discharging compressing tablet, screening, then add in mixer and mix 30min with 5 parts, molecular sieve, discharging packing, had both obtained the finished product.
Above-described embodiment and two kinds of thermo-stabilizer 3 mass parts that do not add molecular sieve are added respectively in 100 mass parts PVC, add again 60 mass parts dimixo-octyl phthalates (DOP), at 140 ℃ mixing 10 minutes, at 100 ℃, be pressed into the thin slice that thickness is 1mm, be cut into the test piece of 1cm * 1cm, under 180 ± 1 ℃ of conditions, do static-aging experiment, experimental result is in Table 1.Wherein embodiment 3 is comparative example.
Table 1
Embodiment 2,3
Above-mentioned molecular sieve stablizer is added in 100 parts of PVC by same amount, add again 60 parts of dimixo-octyl phthalates (DOP), then by GB GB2113-82 " plastics whiteness experimental technique ", three kinds of PVC plastics of preparation are carried out to heat-resisting whiteness experiment.From table 3, can find, prepared novel molecular sieve PVC one package stabilizer is compared with traditional stablizer, has outstanding thermostability.
Table 2: composite thermal stabilizer compositing formula
Wherein: lubricant is selected from polyethylene wax, Tegin 55G or stearic acid; Surface modifier is selected pentaerythritol ester or triphenyl phosphite; Auxiliary heat stabilizer is selected epoxy soybean oil or diphenylpropane-1,3-dione(DPPO).
Table 3: test piece is placed on the relative whiteness value (%) of testing in the whiteness instrument of checking with the standard white body that whiteness is 85%
Claims (2)
1. a molecular sieve PVC one package stabilizer, is characterized in that being comprised of the raw material of following mass percent:
Described lubricant is polyethylene wax, Tegin 55G or stearic acid;
Described surface modifier is pentaerythritol ester or triphenyl phosphite;
Described auxiliary heat stabilizer is epoxy soybean oil or diphenylpropane-1,3-dione(DPPO);
Described molecular sieve makes in accordance with the following steps:
(1) by kaolin roasting 2～3h at 550～650 ℃;
(2) mix with soda ash, make the component mol ratio in solution be controlled at n (H
2o)/n (Na
2o)/n (SiO
2)=1:1.5:2.5, then ageing 2h at 60 ℃;
(3) crystallization 4h under 90 ℃ of hydrothermal conditions;
(4) finally by filtering separation, and to neutrality, be drying to obtain molecular sieve with deionized water wash.
2. the preparation method of a molecular sieve PVC one package stabilizer according to claim 1, it is characterized in that first calcium stearate, Zinic stearas and lubricant being added in reactor and fully being mixed, get mixture, add and in kneader, heat and stir, add surface modifier, at 100～110 ℃, mediate 20min, then in kneader, add auxiliary heat stabilizer to mediate stirring 30min, discharging compressing tablet, screening mix composite afterwards with molecular sieve, packing.
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| CN201010565585.3A CN102477196B (en) | 2010-11-30 | 2010-11-30 | Novel molecular sieve PVC composite stabilizing agent and its preparation method |
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| CN201010565585.3A CN102477196B (en) | 2010-11-30 | 2010-11-30 | Novel molecular sieve PVC composite stabilizing agent and its preparation method |
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| CN102477196B true CN102477196B (en) | 2014-01-29 |
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| Hans Zweifel主编，欧育湘，李建军等译.《塑料添加剂手册》.《塑料添加剂手册》.化学工业出版社,2005,(第五版),第306-307页. * |
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