CN102504340B - Nontoxic calcium and zinc thermal stabilizer - Google Patents
Nontoxic calcium and zinc thermal stabilizer Download PDFInfo
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- CN102504340B CN102504340B CN 201110344592 CN201110344592A CN102504340B CN 102504340 B CN102504340 B CN 102504340B CN 201110344592 CN201110344592 CN 201110344592 CN 201110344592 A CN201110344592 A CN 201110344592A CN 102504340 B CN102504340 B CN 102504340B
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- calcium
- nontoxic
- zinc
- stabilizer
- heat stabilizer
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- 231100000252 nontoxic Toxicity 0.000 title claims abstract description 18
- 230000003000 nontoxic effect Effects 0.000 title claims abstract description 18
- 239000011701 zinc Substances 0.000 title abstract description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title abstract description 12
- 229910052725 zinc Inorganic materials 0.000 title abstract description 12
- 239000011575 calcium Substances 0.000 title abstract description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title abstract description 7
- 229910052791 calcium Inorganic materials 0.000 title abstract description 7
- 239000003017 thermal stabilizer Substances 0.000 title abstract description 4
- 239000003381 stabilizer Substances 0.000 claims abstract description 29
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008117 stearic acid Substances 0.000 claims abstract description 9
- 150000003751 zinc Chemical class 0.000 claims abstract description 6
- 125000005594 diketone group Chemical group 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 17
- 239000012760 heat stabilizer Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- -1 Phosphorous acid ester Chemical class 0.000 claims description 5
- 159000000007 calcium salts Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 3
- 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 2
- 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 2
- PXSUSKMUPNBDSO-UHFFFAOYSA-N 4-methyl-1-phenylpentane-1,3-dione Chemical compound CC(C)C(=O)CC(=O)C1=CC=CC=C1 PXSUSKMUPNBDSO-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- QICVZJNIJUZAGZ-UHFFFAOYSA-N benzene;phosphorous acid Chemical compound OP(O)O.C1=CC=CC=C1 QICVZJNIJUZAGZ-UHFFFAOYSA-N 0.000 claims description 2
- 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 description 2
- 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 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 abstract description 4
- 230000003068 static effect Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 125000000129 anionic group Chemical group 0.000 abstract 2
- 239000000314 lubricant Substances 0.000 abstract 2
- 239000005711 Benzoic acid Substances 0.000 abstract 1
- 235000010233 benzoic acid Nutrition 0.000 abstract 1
- 230000001050 lubricating effect Effects 0.000 abstract 1
- 229920005862 polyol Polymers 0.000 abstract 1
- 150000003077 polyols Chemical class 0.000 abstract 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000344 soap Substances 0.000 description 10
- 239000004800 polyvinyl chloride Substances 0.000 description 8
- 229920000915 polyvinyl chloride Polymers 0.000 description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 235000010216 calcium carbonate Nutrition 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004605 External Lubricant Substances 0.000 description 2
- 239000004610 Internal Lubricant Substances 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- QNNXEUPKHFCUKS-UHFFFAOYSA-J [Ca+2].[Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O Chemical compound [Ca+2].[Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O QNNXEUPKHFCUKS-UHFFFAOYSA-J 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical group [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- ZHALDANPYXAMJF-UHFFFAOYSA-N octadecanoate;tris(2-hydroxyethyl)azanium Chemical group OCC[NH+](CCO)CCO.CCCCCCCCCCCCCCCCCC([O-])=O ZHALDANPYXAMJF-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229940029614 triethanolamine stearate Drugs 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-M benzoate Chemical compound [O-]C(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-M 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005070 sampling Methods 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
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Lubricants (AREA)
Abstract
The invention discloses a nontoxic calcium and zinc thermal stabilizer, which comprises the following matters: a primary calcium and zinc stabilizer, a diketone, a polyol, an external lubricating agent, an internal lubricating agent and an antioxygen. Compared with the prior art, the one-pot-process chemical mixing for synthesizing a calcium and zinc salt, which is mixing on a molecular level, has better synergetic effect than physical mixing; the introduction of another anionic benzoic acid on the basis of one anionic stearic acid greatly improves the processing properties of the stabilizer, such as lubricating property, transparent property and compatibility; without any toxic components, the mixture is really nontoxic and environment-friendly; the prepared thermal stabilizer has high static performance, dynamic performance and color constancy; and at 180 DEG C, the congo red time is more than 120 minutes, and the white difference delta E between two rolled pieces is less than 2. The production process is simple and the cost is low.
Description
Technical field
The invention belongs to thermo-stabilizer, belong to especially the nontoxic calcium zinc heat stabilizer for polyvinyl chloride.
Background technology
Polyvinyl chloride (PVC) is one of five general in the world large synthetic resins, and consumption is maximum, and it has superior performance and is widely used in the every field such as construction industry, agricultural, daily necessities.During due to PVC high temperature, processing heat stability is poor, must add thermo-stabilizer to keep its performance when its forming process, and thermo-stabilizer commonly used mainly contains the stablizers such as lead salts, organic tin, rare earth class and metal soap.Lead salt stabilizer is cheap, thermostable effect good, amount ratio is larger, but its toxicity is large, serious harm HUMAN HEALTH and contaminate environment, recent two decades, along with the requirement of environmental protection, the toxic metal such as that western countries forbid is leaded in thermo-stabilizer, cadmium, and promulgate that command request forbade selling at EU market the equipment that contains lead, mercury, cadmium, chromium, Polybrominated biphenyl and 6 kinds of objectionable impuritiess of polybromodiphenyl ether from 1 day July in 2006; Therefore, nontoxic, pollution-free, the compound and efficient development topic that has become the PVC thermo-stabilizer, nontoxic Ca/Zn thermo-stabilizer are nontoxic, the environment-friendly type thermo-stabilizers of generally acknowledging in the world, have extremely wide development space.The less stable of Zn soap stablizer to PVC, belong to fugitive thermo-stabilizer, and " zinc burning " (be mainly that the ZnCl2 that produces is strong lewis acid, have the effect that HCl is taken off in catalysis) phenomenon easily occurs, but have the advantages such as initial coloring is good, weathering resistance is strong.Ca soap thermo-stabilizer belongs to long-acting thermo-stabilizer, less stable, and tint permanence is strong, but nontoxic, has good oilness.The Ca/Zn composite thermal stabilizer is exactly the synergistic effect of utilizing both to have, make it become in recent years most active research field in one package stabilizer, the people such as picture Liu Diqiang have mentioned the composite of calcium stearate zinc salt in patent " a kind of environmental protection pvc calcium zinc stabilizer ", the Li Jian of Wuhu conch company, the people such as Wang Yanglin disclose a kind of calcium-zinc composite stabilizing agent in patent, the formula that relates to the calcium stearate zinc salt has well replaced traditional poisonous stablizer.This patent is further combined with the performance characteristics separately of benzoate anion and stearate radical, then stablizes characteristics in conjunction with the shot and long term of calcium zinc, uses one pot reaction, and is simple and easy to operate, superior performance, the constraint that the performance of the simple stearate that breaks traditions is single.Every kind of material performance characteristics separately on the molecule rank, the nontoxic calcium zinc heat stabilizer of same-action.
Summary of the invention
The object of the present invention is to provide a kind of novel nontoxic calcium zinc stablizer, realized the synergistic effect between each component of stablizer, solved stablizer poor in processability and the single shortcoming of stability, extended steady time.
The technical scheme of technical solution problem of the present invention is: a kind of nontoxic calcium zinc heat stabilizer, contain the material of following weight part:
In order further to strengthen the property and to study more favourable formula, can add following one or more;
Phosphorous acid ester 5～10
Epoxy compounds 10～20
Hydrotalcite 5～15
Described main calcium zinc stabilizer prepares by the following method:
A) stearic acid and phenylformic acid are added in reaction vessel, be warming up to 80～90 ℃, until melt fully, obtain mixed solution A;
B) be that the sodium hydroxide solution of 15%-25% is added drop-wise in the prepared mixed solution A of a) operation with weight concentration, after dripping off, then stirred 0.5-1 hour; Be warming up to 95 ℃, then drip zinc salt and calcium salt, after dripping off, then stirred 1-1.5 hour, be cooled to room temperature, product is washed with water, suction filtration is dried to constant weight in 60-80 ℃; The mol ratio of stearic acid, phenylformic acid, sodium hydroxide, zinc salt, calcium salt is 1-2: 1-2: 2-4: 0.5-1: 0.5-1;
Described zinc salt is zinc sulfate, zinc chloride, all technical grade.
Described calcium salt is calcium sulfate, calcium chloride, all technical grade.
Described diketone is stearoyl benzoyl methane, isobutyryl benzoyl methane and phenyl phenacyl ketone.
Described polyvalent alcohol is tetramethylolmethane, sorbyl alcohol;
Described phosphorous acid ester is triphenyl phosphite, the different monooctyl ester of triphosphoric acid three, phosphorous acid benzene di-isooctyl;
Described epoxy compounds is epoxy soybean oil;
Described external lubricant is triethanolamine stearate;
Described internal lubricant is PE wax;
Described oxidation inhibitor is Hinered phenols;
When zinc soap during as thermo-stabilizer, because the electronegativity of metallic element zn is larger, attract electronic capability stronger, can form coordinate bond with unsettled chlorallylene in polyvinyl chloride resin, and the negatively charged ion that makes metallic soap replaces the unstable chlorine atom, alleviated PVC and removed the speed of reaction that DeR occurs HCl, so generally have initial stage form and aspect preferably.But when occuring, substitution reaction has ZnCI
2Generate.ZnCl
2As a kind of Lewis acid, cause ' the zinc burning " phenomenon.When zinc soap and calcium soap synergy during as thermo-stabilizer, ZnCl
2, the chlorine atom can and the calcium soap ligand between exchange, regenerate zinc soap and can not promote to take off the CaCl of HCl
2, delay ZnCl in the PVC parent
2, appearance, suppress " zinc burning ".In addition, calcium soap itself can also play the effect of absorbing HCl as a kind of long-acting type thermo-stabilizer in the reaction later stage, and long-term thermal stability is improved.
the present invention compared with prior art, adopt the synthetic calcium zinc salt of chemical mixing of one kettle way than physical mixed, because it is the mixing on molecular level, synergistic effect is better, introduce again another negatively charged ion phenylformic acid on a kind of negatively charged ion stearic basis, make the oilness of stablizer, the transparency, the processing characteristicies such as consistency are greatly improved, in mixture without any poisonous composition, really accomplished asepsis environment-protecting, made thermo-stabilizer has good nature static, dynamic and hold look, under 180 ℃, the Congo red time is greater than 120min, the poor Δ E of the whiteness of two roll tablets＜2.Production technique is simple, and cost is low.
Embodiment
The present invention is described in detail below in conjunction with embodiment.
Embodiment 1:
The preparation of main stabilizer;
A) stearic acid and the 0.05mol phenylformic acid with 0.05mol adds in the 1000ml three-necked flask, is warming up to 70 ℃, until melt fully.
B) sodium hydroxide (slightly excessive) with 0.1mol is dissolved in the beaker of 100ml, dropwise adds there-necked flask with dropping funnel, drips off in ten minutes, keeps this and reacts half hour.
C) temperature is risen to 85 ℃, the Zinc vitriol and the 0.025mol calcium chloride that then take 0.025mol add the 50ml beaker to dissolve fully, add simultaneously respectively zinc sulfate and calcium chloride with dropping funnel, and half hour drips off, and keep this reaction 1 hour.
E) product is washed with water, suction filtration, the baking oven that is placed on 80 ℃ was dried to constant weight in interior 12 hours.
Embodiment 2
The preparation of main stabilizer:
A) stearic acid and the 0.05mol phenylformic acid with 0.05mol adds in the 1000ml three-necked flask, is warming up to 80～90 ℃, until melt fully.
B) sodium hydroxide (slightly excessive) with 0.1mol is dissolved in the beaker of 100ml, dropwise adds there-necked flask with dropping funnel, drips off in ten minutes, keeps this and reacts half hour.
C) temperature is risen to 95 ℃, then the zinc chloride that takes 0.025mol dissolves fully with dropping funnel and first adds in flask, then takes 0.025mol calcium chloride and adds the 50ml beaker to dissolve fully, adds respectively with dropping funnel, half hour, drip off, and keeps at last this reaction 1 hour.
E) product is washed with water, suction filtration, the baking oven that is placed on 80 ℃ was dried to constant weight in interior 12 hours.
Embodiment 3
The preparation of main stabilizer:
A) stearic acid and the 0.1mol phenylformic acid with 0.05mol adds in the 1000ml three-necked flask, is warming up to 80～90 ℃, until melt fully.
B) sodium hydroxide (slightly excessive) with 0.15mol is dissolved in the beaker of 100ml, adds there-necked flask with dropping funnel, drips off in ten minutes, keeps this and reacts half hour.
C) temperature is risen to 95 ℃, then the calcium chloride that takes 0.03mol dissolves fully and first adds in flask with dropping funnel, then taking the 0.03mol Zinc vitriol adds the 50ml beaker to dissolve fully, add respectively with dropping funnel, controlling respectively half hour drips off, and keeps at last this reaction 1 hour.
E) product is washed with water, suction filtration, the baking oven that is placed on 80 ℃ was dried to constant weight in interior 12 hours.
Embodiment 4
The preparation of main stabilizer:
A) stearic acid and the 0.05mol phenylformic acid with 0.1mol adds in the 1000ml three-necked flask, is warming up to 80～90 ℃, until melt fully.
B) sodium hydroxide with 0.15mol is dissolved in the beaker of 100ml, dropwise adds there-necked flask with dropping funnel, drips off in ten minutes, keeps this and reacts half hour.
C) temperature is risen to 95 ℃, then take Zinc vitriol and the 0.03mol of 0.03mol, Calcium hydrogen carbonate adds the 50ml beaker to dissolve fully, add simultaneously respectively zinc sulfate and Calcium hydrogen carbonate with dropping funnel, half hour, drip off, keep at last this reaction 0.5 hour, add at last 0.05mol sodium hydroxide, reaction was kept 1 hour;
E) product is washed with water, suction filtration, the baking oven that is placed on 80 ℃ was dried to constant weight in interior 12 hours.
Embodiment 5
Phosphorous acid ester of the present invention is produced by Milan, Nanjing chemical industry company limited.
Embodiment 6
Embodiment 7
Embodiment 8
Embodiment 9
Embodiment 10
Embodiment 11
The described external lubricant of above-mentioned patent is triethanolamine stearate, and internal lubricant PE wax, oxidation inhibitor are that Hinered phenols (is produced by Jin Hai Albemarle Corporation.
With 50g pvc, titanium white 1g, new stabilizer (embodiment 5-11) 2g, fine particle calcium carbonate 20g, dioctyl phthalate (DOP) 20ml, drop in agitator, fully stirred ten minutes, then carry out the stable examination of Dynamic Thermal, this Dynamic Thermal stablizer test is carried out compressing tablet at the double roller plastic-making device (east, Shanghai Weir motor company) of 180 ℃ ± 5 ℃, roller diameter 110cm, constant roll temperature is opened refining continuously, begin sampling after embracing roller, after this got a sample every five minutes, get at last first compressing tablet of five minutes and carry out the steady stability test.
Its result is as shown in table 1:
The example whiteness value of compressing tablet day part
The above results shows that the whiteness of example 5 is best, in conjunction with cost, and example 7, the stablizer synergistic effect of example 9 formulas is good, and dynamic effect is best.In the situation that basic components adds different auxiliary stabilizers and different weight parts, its stability is also different.
Static Congo red test is in 180 ℃ of oil baths, and 2917-82 detects according to standard GB/T.Its result is as shown in table 2:
Table 2:
| Sample | Embodiment 9 | Embodiment 7 | Embodiment 8 | Embodiment 10 | Embodiment 6 | Embodiment 5 | Embodiment 11 |
| min | 124 | 133 | 131 | 118 | 134 | 156 | 120 |
The above results shows: the formula steady stability performance of example 5 is because main stabilizer content is many, and effect is best, but other embodiment steady time is also far away higher than static Congo red test duration of simple stearate.
Claims (6)
1. nontoxic calcium zinc heat stabilizer, contain the material of following weight part:
Described main calcium zinc stabilizer prepares by the following method:
A) stearic acid and phenylformic acid are added in reaction vessel, be warming up to 80～90 ℃, until melt fully, obtain mixed solution A;
B) be that the sodium hydroxide solution of 15%-25% is added drop-wise in the prepared mixed solution A of a) operation with weight concentration, after dripping off, then stirred 0.5-1 hour; Be warming up to 95 ℃, then drip zinc salt and calcium salt, after dripping off, then stirred 1-1.5 hour, be cooled to room temperature, product is washed with water, suction filtration is dried to constant weight in 60-80 ℃; The mol ratio of stearic acid, phenylformic acid, sodium hydroxide, zinc salt, calcium salt is 1-2:1-2:2-4:0.5-1:0.5-1.
2. a kind of nontoxic calcium zinc heat stabilizer according to claim 1 is characterized in that: the material that can also add following one or more weight parts:
Phosphorous acid ester 5 ~ 10
Epoxy compounds 10 ~ 20
Hydrotalcite 5 ~ 15.
3. a kind of nontoxic calcium zinc heat stabilizer according to claim 1 is characterized in that:
Described diketone is stearoyl benzoyl methane, isobutyryl benzoyl methane or phenyl phenacyl ketone.
4. a kind of nontoxic calcium zinc heat stabilizer according to claim 1 is characterized in that:
Described polyvalent alcohol is Ji Wusi or sorbyl alcohol.
5. a kind of nontoxic calcium zinc heat stabilizer according to claim 2 is characterized in that:
Described phosphorous acid ester is triphenyl phosphite or phosphorous acid benzene di-isooctyl.
6. a kind of nontoxic calcium zinc heat stabilizer according to claim 2 is characterized in that:
Described epoxy compounds is epoxy soybean oil.
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| CN103665635B (en) * | 2013-11-25 | 2015-10-21 | 安徽师范大学 | A kind of electric wire non-toxic stabilizer |
| CN103694599A (en) * | 2013-12-11 | 2014-04-02 | 甘肃大禹节水集团股份有限公司 | Efficient and environment-friendly polyvinyl chloride heat stabilizer and preparation method thereof |
| CN105237911A (en) * | 2015-11-01 | 2016-01-13 | 吕小方 | Heat stabilizer |
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| CN105385072B (en) * | 2015-12-23 | 2018-02-23 | 广东信诚达科技有限公司 | PVC calcium zinc heat stabilizers and its auxiliary heat stabilizer |
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| CN113929966A (en) * | 2021-10-27 | 2022-01-14 | 浙江知友塑料科技有限公司 | Formula and production process of high-stability liquid calcium-zinc stabilizer |
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