CN114573925A - Preparation method of organic rare earth composite stabilizer for PVC - Google Patents
Preparation method of organic rare earth composite stabilizer for PVC Download PDFInfo
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- CN114573925A CN114573925A CN202210260917.XA CN202210260917A CN114573925A CN 114573925 A CN114573925 A CN 114573925A CN 202210260917 A CN202210260917 A CN 202210260917A CN 114573925 A CN114573925 A CN 114573925A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 43
- 239000006084 composite stabilizer Substances 0.000 title claims abstract description 37
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003381 stabilizer Substances 0.000 claims abstract description 28
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 26
- -1 rare earth salt Chemical class 0.000 claims abstract description 23
- 150000008301 phosphite esters Chemical class 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000004593 Epoxy Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 58
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000003921 oil Substances 0.000 claims description 32
- 235000019198 oils Nutrition 0.000 claims description 32
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 28
- 239000000194 fatty acid Substances 0.000 claims description 28
- 229930195729 fatty acid Natural products 0.000 claims description 28
- 150000002603 lanthanum Chemical class 0.000 claims description 21
- 150000000703 Cerium Chemical class 0.000 claims description 20
- 150000004665 fatty acids Chemical class 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 12
- 239000000314 lubricant Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 125000005594 diketone group Chemical group 0.000 claims description 8
- 235000012424 soybean oil Nutrition 0.000 claims description 8
- 239000003549 soybean oil Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 239000002131 composite material Substances 0.000 claims description 3
- GPOGLVDBOFRHDV-UHFFFAOYSA-N (2-nonylphenyl) dihydrogen phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(O)O GPOGLVDBOFRHDV-UHFFFAOYSA-N 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 claims description 2
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical compound [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 0.000 abstract description 9
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 34
- 229920000915 polyvinyl chloride Polymers 0.000 description 34
- 239000000203 mixture Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 231100000252 nontoxic Toxicity 0.000 description 6
- 230000003000 nontoxic effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000009472 formulation Methods 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- MALCFCAHLMXZNC-UHFFFAOYSA-N P(OCCCCCC(C)C)(OCCCCCC(C)C)O.C1=CC=CC=C1 Chemical compound P(OCCCCCC(C)C)(OCCCCCC(C)C)O.C1=CC=CC=C1 MALCFCAHLMXZNC-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a preparation method of an organic rare earth composite stabilizer for PVC, belonging to the technical field of stabilizers, and the preparation method comprises the following components by equal mass: 80-90 parts of organic rare earth salt, 1-10 parts of auxiliary agent, 1-10 parts of phosphite ester, 1-5 parts of epoxy compound and 1-10 parts of auxiliary heat stabilizer; by adopting the organic rare earth to be compounded with the auxiliary stabilizer and other additives, the defect of zinc burning of the calcium-zinc composite stabilizer is overcome, and the production cost of the stabilizer is reduced on the basis of not influencing the transparency and the thermal stability; the composite stabilizer prepared by the method has good light stability, low cost and good long-term stability, can partially replace organic tin and completely replace calcium zinc and barium zinc stabilizers, and has great advantages in PVC transparent product application.
Description
Technical Field
The invention relates to the technical field of stabilizers, in particular to a preparation method of an organic rare earth composite stabilizer for PVC.
Background
PVC is a heat sensitive resin that has only been second-ranked in world-year sales among thermoplastics than PE. The product has the advantages of easy regulation of hardness, high mechanical property, corrosion resistance, good electrical insulation, high transparency and the like, and has the conditions of low price, rich resources, mature manufacturing process and the like, so the product has very wide application in the production fields of industry, agriculture and the like. However, polyvinyl chloride has poor stability to light and heat, begins to decompose at about 160 ℃ to generate hydrogen chloride, and the released hydrogen chloride accelerates the decomposition of PVC to cause discoloration, and the physical and mechanical properties thereof are rapidly deteriorated. PVC is generally processed at temperatures above 160 ℃ and it is therefore necessary in practice to add stabilizers to improve its stability to heat and light.
PVC heat stabilizers in the prior art mainly include: lead salt stabilizer, organic tin stabilizer, organic antimony stabilizer and metal soap composite stabilizer. The lead salt stabilizer is efficient and cheap, but causes environmental pollution, and has the characteristic that transparent products cannot be applied; the organotin stabilizer with excellent performance has the defect of high price; the organic antimony stabilizer has poor light stability and weather resistance, and the outdoor use is limited; the metal soap composite stabilizer also has the defects of low long-term stability efficiency, poor transparency, easy occurrence of 'zinc burning' and the like. Aiming at the defects in the prior art, the invention aims to provide the organic rare earth composite stabilizer for PVC and the preparation method thereof, so that the heat stabilizer has the properties of strong thermal stability, no toxicity, no pollution, no odor, no sulfide pollution, environmental protection and the like.
Disclosure of Invention
The invention aims to solve the problems that a heat stabilizer in the prior art has no properties of strong thermal stability, no toxicity, no pollution, no odor, no sulfuration pollution, environmental protection and the like, and provides a preparation method of an organic rare earth composite stabilizer for PVC.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an organic rare earth composite stabilizer for PVC comprises the following components by mass: 80-90 parts of organic rare earth salt, 1-10 parts of auxiliary agent, 1-10 parts of phosphite ester, 1-5 parts of epoxy compound and 1-10 parts of auxiliary heat stabilizer.
Preferably, the organic rare earth salt is one or two of organic lanthanum salt and organic cerium salt.
Preferably, the organic lanthanum salt comprises the following components: 50-60 parts of fatty acid, 20-30 parts of sodium hydroxide solution with the mass concentration of 10% -15%, 10-15 parts of lanthanum chloride solution and 3-5 parts of solvent;
the preparation method of the organic lanthanum salt comprises the following steps:
a1, putting fatty acid into a reaction kettle, and heating to 50-80 ℃;
a2, dropwise adding 10-15% sodium hydroxide solution in mass concentration into the reaction kettle, and measuring and controlling the pH value to be 6-7;
a3, keeping the temperature at 50-80 ℃ for 1-2h for full reaction;
a4, adding a lanthanum chloride solution into a reaction kettle, and controlling the temperature to be 50-70 ℃ and preserving heat for 1-3h for full reaction;
a5, standing and layering for 1-3 h;
a6, separating an organic oil phase product in the reaction kettle;
a7, adding solvent oil into the water layer to extract oil phase products;
a8, combining the oil phase products obtained in the step A6 and the step A7 and carrying out vacuum drying treatment;
a9, taking the product after vacuum drying to obtain the organic lanthanum salt.
Preferably, the organic cerium salt comprises the following components: 50-60 parts of fatty acid, 20-30 parts of sodium hydroxide solution with the mass concentration of 10% -15%, 10-15 parts of lanthanum chloride solution and 3-5 parts of solvent;
the preparation steps of the organic cerium salt are as follows:
b1, putting fatty acid into a reaction kettle, and heating to 50-80 ℃;
b2, dropwise adding 10-15% sodium hydroxide solution in mass concentration into the reaction kettle, and measuring and controlling the pH value to be 6-7;
b3, keeping the temperature at 50-80 ℃ for 1-2h for full reaction;
b4, adding a cerium chloride solution into the reaction kettle, and controlling the temperature to be 50-70 ℃ and preserving the heat for 1-3h for full reaction;
b5, standing and layering for 1-3 h;
b6, separating an organic oil phase product in the reaction kettle;
b7, adding solvent oil into the water layer to extract an oil phase product;
b8, combining the oil phase products obtained in the step B6 and the step B7 and carrying out vacuum drying treatment;
b9, taking the product after vacuum drying to obtain the organic cerium salt.
Preferably, the adjuvant is a lubricant.
Preferably, the lubricant is any one of fatty acid, dicarboxylic acid ester, fatty acid ester, polyol fatty acid ester, high molecular weight complex ester, and silicone oil.
Preferably, the phosphite ester is one or two of monobenzene diisooctyl phosphite, diphenyl diisooctyl phosphite, triphenyl phosphite, triisodecyl phosphite and nonyl phenol phosphite.
Preferably, the epoxy compound is epoxidized soybean oil, epoxidized fatty acid, epoxy ether.
Preferably, the auxiliary heat stabilizer is one or more than two of beta diketone, fatty acid zinc or organic tin.
Preferably, the method comprises the following steps:
s1, putting one or two of organic cerium salt and organic lanthanum salt into a reaction kettle;
s2, putting the lubricant, the phosphite ester, the epoxy compound and the auxiliary heat stabilizer into a reaction kettle;
s3, fully stirring and mixing for 1-2 h;
s4, heating to 40-50 ℃ and reacting for 2-3 h;
and S5, fully mixing and reacting to obtain the stabilizer.
Compared with the prior art, the invention provides a preparation method of an organic rare earth composite stabilizer for PVC, which has the following beneficial effects:
according to the preparation method of the organic rare earth composite stabilizer, the organic rare earth is compounded with the auxiliary stabilizer and other additives, so that the defect of zinc burning of the calcium-zinc composite stabilizer is overcome, and the production cost of the stabilizer is reduced on the basis of not influencing the transparency and the thermal stability; the composite stabilizer prepared by the method has good light stability, low cost and good long-term stability, can partially replace organic tin and completely replace calcium zinc and barium zinc stabilizers, and has great advantages in PVC transparent product application.
Drawings
FIG. 1 is a graph showing the B-value ratio of PVC containing the heat stabilizer of the present invention in place of 50% organotin;
FIG. 2 is a B-value comparison graph of PVC containing the heat stabilizer of the present invention in place of 100% liquid barium zinc.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.
Example 1:
a preparation method of an organic rare earth composite stabilizer for PVC comprises the following components by equal mass: 80 parts of organic rare earth salt, 2 parts of auxiliary agent, 6 parts of phosphite ester, 4 parts of epoxy compound and 8 parts of auxiliary heat stabilizer.
The organic rare earth salt is a mixture of organic lanthanum salt and organic cerium salt,
the organic lanthanum salt comprises the following components: 55 parts of fatty acid, 25 parts of 12% sodium hydroxide solution, 12 parts of lanthanum chloride solution and 4 parts of solvent;
the preparation steps of the organic lanthanum salt are as follows:
a1, putting 167g of oleic acid and 85g of isooctanoic acid into a reaction kettle, and heating to 60 ℃;
a2, dropwise adding 450ml of sodium hydroxide solution with the concentration of 12% by mass into the reaction kettle, and measuring and controlling the pH value to be 7;
a3, keeping the temperature at 60 ℃ for 1h for full reaction;
a4, adding 140ml of 364g/L lanthanum chloride solution into a reaction kettle, and keeping the temperature at 60 ℃ for 2 hours for full reaction;
a5, standing and layering for 2 h;
a6, separating an organic oil phase product in the reaction kettle;
a7, adding 50g No. 100 solvent oil into the water layer to extract oil phase products;
a8, combining the oil phase products obtained in the step A6 and the step A7, and performing vacuum drying treatment at 80 ℃;
a9, taking the product after vacuum drying to obtain the organic lanthanum salt.
The organic cerium salt comprises the following components: 55 parts of fatty acid, 25 parts of 12% sodium hydroxide solution, 12 parts of lanthanum chloride solution and 4 parts of solvent;
the preparation steps of the organic cerium salt are as follows:
b1, putting 167g of oleic acid and 85g of isooctanoic acid into a reaction kettle, and heating to 60 ℃;
b2, dropwise adding 450ml of sodium hydroxide solution with the concentration of 12% by mass into the reaction kettle, and measuring and controlling the pH value to be 7;
b3, keeping the temperature at 60 ℃ for 1h for full reaction;
b4, adding 70ml of a cerium chloride solution with the concentration of 343g/L into the reaction kettle, and controlling the temperature to be 60 ℃ and preserving heat for 2 hours for full reaction;
b5, standing and layering for 2 h;
b6, separating an organic oil phase product in the reaction kettle;
b7, adding solvent oil into the water layer to extract oil phase products;
b8, combining the oil phase products obtained in the step B6 and the step B7, and performing vacuum drying treatment at 80 ℃;
and B9, taking the product after vacuum drying to obtain the organic cerium salt.
The auxiliary agent is a lubricant.
The lubricant is ZG70L fatty acid compound ester.
The phosphite ester is 8601 nontoxic phosphite ester.
The epoxide compound is 8605 epoxidized soybean oil.
The auxiliary heat stabilizer is DBM-83 beta diketone.
The method for preparing the organic rare earth composite stabilizer comprises the following steps:
s1, placing 80 parts of the mixture of organic cerium salt and organic lanthanum salt into a reaction kettle;
s2, putting 2 parts of ZG70L fatty acid compound ester, 6 parts of 8601 nontoxic phosphite ester, 4 parts of 8605 epoxidized soybean oil and 8 parts of DBM-83 beta diketone into a reaction kettle;
s3, fully stirring and mixing for 2 h;
s4, heating to 40 ℃ and reacting for 2 h;
and S5, fully mixing and reacting to obtain the stabilizer.
Example 2:
a preparation method of an organic rare earth composite stabilizer for PVC comprises the following components by equal mass: 80 parts of organic rare earth salt, 3 parts of auxiliary agent, 6 parts of phosphite ester, 4 parts of epoxy compound and 7 parts of auxiliary heat stabilizer.
The organic rare earth salt is organic lanthanum salt,
the organic lanthanum salt comprises the following components: 55 parts of fatty acid, 25 parts of 12% sodium hydroxide solution, 12 parts of lanthanum chloride solution and 4 parts of solvent;
the preparation steps of the organic lanthanum salt are as follows:
a1, taking 92g of octyl and decyl acid and 105g of p-tert-butyl benzoic acid, putting into a reaction kettle, and heating to 60 ℃;
a2, dripping 450ml of sodium hydroxide solution with the concentration of 12% by mass into the reaction kettle, and measuring and controlling the pH value to be 7;
a3, keeping the temperature at 60 ℃ for 1h for full reaction;
a4, adding 140ml of 364g/L lanthanum chloride solution into a reaction kettle, and keeping the temperature at 60 ℃ for 2 hours for full reaction;
a5, standing and layering for 2 h;
a6, separating an organic oil phase product in the reaction kettle;
a7, adding 50g No. 100 solvent oil into the water layer to extract oil phase products;
a8, combining the oil phase products obtained in the step A6 and the step A7, and performing vacuum drying treatment at 80 ℃;
a9, taking the product after vacuum drying to obtain the organic lanthanum salt.
The auxiliary agent is a lubricant.
The lubricant is ZG70L fatty acid compound ester.
The phosphite ester is 8601 nontoxic phosphite ester.
The epoxy compound is 8605 epoxidized soybean oil.
The auxiliary heat stabilizer is DBM-83 beta diketone.
The method for preparing the organic rare earth composite stabilizer comprises the following steps:
s1, taking 80 parts of organic lanthanum salt mixture and putting the mixture into a reaction kettle;
s2, putting 3 parts of ZG70L fatty acid composite ester, 6 parts of 8601 nontoxic phosphite ester, 4 parts of 8605 epoxidized soybean oil and 7 parts of DBM-83 beta diketone into a reaction kettle;
s3, fully stirring and mixing for 2 h;
s4, heating to 40 ℃ and reacting for 2 h;
and S5, fully mixing and reacting to obtain the stabilizer.
Example 3:
a preparation method of an organic rare earth composite stabilizer for PVC comprises the following components by equal mass: 85 parts of organic rare earth salt, 3 parts of auxiliary agent, 4 parts of phosphite ester, 2 parts of epoxy compound and 6 parts of auxiliary heat stabilizer.
The organic rare earth salt is organic cerium salt.
The organic cerium salt comprises the following components: 55 parts of fatty acid, 25 parts of 12% sodium hydroxide solution, 12 parts of lanthanum chloride solution and 4 parts of solvent;
the preparation method of the organic cerium salt comprises the following steps:
b1, taking 162g of oleic acid and 105g of p-tert-butyl benzoic acid, putting into a reaction kettle, and heating to 60 ℃;
b2, dropwise adding 450ml of sodium hydroxide solution with the concentration of 12% by mass into the reaction kettle, and measuring and controlling the pH value to be 7;
b3, keeping the temperature at 60 ℃ for 1h for full reaction;
b4, adding 70ml of cerium chloride solution with the concentration of 343g/L into the reaction kettle, and controlling the temperature to be 60 ℃ and preserving the heat for 2 hours for full reaction;
b5, standing and layering for 2 h;
b6, separating an organic oil phase product in the reaction kettle;
b7, adding solvent oil into the water layer to extract oil phase products;
b8, combining the oil phase products obtained in the step B6 and the step B7, and performing vacuum drying treatment at 80 ℃;
and B9, taking the product after vacuum drying to obtain the organic cerium salt.
The auxiliary agent is a lubricant.
The lubricant is ZG70L fatty acid compound ester.
The phosphite ester is 8601 nontoxic phosphite ester.
The epoxide compound is 8605 epoxidized soybean oil.
The auxiliary heat stabilizer is DBM-83 beta diketone.
The method for preparing the organic rare earth composite stabilizer comprises the following steps:
s1, putting 85 parts of the mixture of organic cerium salt and organic lanthanum salt into a reaction kettle;
s2, putting 3 parts of ZG70L fatty acid composite ester, 4 parts of 8601 nontoxic phosphite ester, 2 parts of 8605 epoxidized soybean oil and 6 parts of DBM-83 beta diketone into a reaction kettle;
s3, fully stirring and mixing for 2 h;
s4, heating to 40 ℃ and reacting for 2 h;
and S5, fully mixing and reacting to obtain the stabilizer.
The stabilizer is tested by combining the above embodiments, and the specific test flow and test results are as follows:
testing one:
the stability of PVC containing the heat stabilizer of example 1 according to the invention was determined on a two-roll mill.
The formulation of the PVC rigid sheet is shown in table 1:
TABLE 1
According to the comparative formula of the PVC hard sheet test in the table 1, the components are accurately weighed and mixed uniformly. It was introduced into a two-roll mill and plasticated at 200 ℃ at 17/15rpm, with a feed quantity of 200 g. Taking a sample piece every 3min, wherein the B value can represent the degradation discoloration degree of the PVC melt in the mixing process, and the smaller the B value, the better the stabilizing effect of the stabilizer. The colorimeter used was of the type HP200, illuminant: D65.
formulation No. 1 is the heat stabilizer of example 1 instead of 50% of the organotin heat stabilizer, and formulation No. 2 is the organotin heat stabilizer, as a control. The organotin stabilizer used was JX-181, the tin content being 19.2%. The results are shown in Table 2:
TABLE 2
Corresponding to Table 2, the B values of the experimental samples are plotted against the B values, as shown in FIG. 1. The ordinate is the B value of the PVC sample measured by a color difference meter, the abscissa is the sampling time of the PVC sample, and the curve represents the change relation of the B value of the PVC melt along with the melting time.
As can be seen from Table 2 and FIG. 1, the 3min formula No. 1B value is smaller than the formula No. 2, the 6min, 9min and 12min B values are basically the same, the stability is equivalent, the 15min formula No. 1B value is larger than the formula No. 2, and the stability at the later stage is slightly worse than that of pure base tin. Therefore, the stability of the organic rare earth composite stabilizer obtained by the invention can be used for processing PVC hard rolled sheets.
And (2) testing:
the stability of the PVC containing the heat stabilizer of example 2 was determined using a two-roll mill. The formulation of the PVC flexible article is shown in Table 3.
TABLE 3
According to the comparative formula of the PVC soft product test in the table 3, the components are accurately weighed and mixed uniformly. This was added to a two-roll mill and plasticated at 170 ℃ at 17/15rpm with a feed of 200g and plasticated for 3min for static stability comparison. Setting the temperature of the rotary oven at 190 ℃, placing the plasticated sample wafer into the rotary oven, and taking out one sample wafer from the rotary oven every 10min, wherein the B value can represent the degradation and color change degree of the PVC soft sample wafer at static high temperature, and the smaller the B value, the better the stabilizing effect of the stabilizer. The rotary oven is YB-881-IG type, the type of the color difference instrument is HP200, and the light source: D65.
formula No. 3 is the example 2 heat stabilizer instead of the liquid barium zinc heat stabilizer, and formula No. 4 is the liquid barium zinc heat stabilizer as a control. The used liquid barium zinc stabilizer is BZ-901, and the metal content is 10.2%. The results are shown in Table 4.
TABLE 4
Corresponding to Table 4, the B value of the experimental sample is plotted against the comparative value, as shown in FIG. 2. The ordinate is the B value of the PVC sample wafer measured by a color difference meter, the abscissa is the sampling time of the PVC sample wafer, and the curve represents the change relation of the B value of the PVC melt along with the static baking time.
As can be seen from Table 4 and FIG. 2, the B value of formula No. 3 is smaller than that of formula No. 4 before 60min, the static stability of formula No. 3 is better than that of formula No. 4, the scorching phenomenon already occurs in formula No. 4 after 60min, and the formula No. 3 is only yellowed seriously and is not scorched. Formula No. 3 has better stability than liquid barium zinc. Therefore, the organic rare earth composite stabilizer obtained by the invention can completely replace liquid barium zinc to be applied to soft PVC products.
Accordingly, the organic rare earth composite stabilizer of example 3 was tested, and the results were substantially identical to those of example 2.
As can be seen from tables 1 and 2 and examples 1 to 3, the defect of zinc burning of the calcium-zinc composite stabilizer is overcome by adopting the organic rare earth to compound with the auxiliary stabilizer and other additives, and the production cost of the stabilizer is reduced on the basis of not influencing the transparency and the thermal stability; the composite stabilizer prepared by the method has good light stability, low cost and good long-term stability, can partially replace organic tin and completely replace calcium zinc and barium zinc stabilizers, and has great advantages in PVC transparent product application.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical scope of the present invention and the equivalent alternatives or modifications according to the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (10)
1. The preparation method of the organic rare earth composite stabilizer for PVC is characterized in that the organic rare earth composite stabilizer comprises the following components in parts by mass: 80-90 parts of organic rare earth salt, 1-10 parts of auxiliary agent, 1-10 parts of phosphite ester, 1-5 parts of epoxy compound and 1-10 parts of auxiliary heat stabilizer.
2. The method for preparing an organic rare earth composite stabilizer according to claim 1, wherein the organic rare earth salt is one or both of an organic lanthanum salt and an organic cerium salt.
3. The method for preparing an organic rare earth composite stabilizer according to claim 2, wherein the organic lanthanum salt comprises the following components: 50-60 parts of fatty acid, 20-30 parts of sodium hydroxide solution with the mass concentration of 10% -15%, 10-15 parts of lanthanum chloride solution and 3-5 parts of solvent;
the preparation steps of the organic lanthanum salt are as follows:
a1, putting fatty acid into a reaction kettle, and heating to 50-80 ℃;
a2, dropwise adding 10-15% sodium hydroxide solution in mass concentration into the reaction kettle, and measuring and controlling the pH value to be 6-7;
a3, keeping the temperature at 50-80 ℃ for 1-2h for full reaction;
a4, adding a lanthanum chloride solution into a reaction kettle, and controlling the temperature to be 50-70 ℃ and preserving heat for 1-3h for full reaction;
a5, standing and layering for 1-3 h;
a6, separating an organic oil phase product in the reaction kettle;
a7, adding solvent oil into the water layer to extract oil phase products;
a8, combining the oil phase products obtained in the step A6 and the step A7 and carrying out vacuum drying treatment;
a9, taking the product after vacuum drying to obtain the organic lanthanum salt.
4. The method of preparing the organic rare earth composite stabilizer according to claim 2, wherein the organic cerium salt comprises the following components: 50-60 parts of fatty acid, 20-30 parts of sodium hydroxide solution with the mass concentration of 10% -15%, 10-15 parts of lanthanum chloride solution and 3-5 parts of solvent;
the preparation steps of the organic cerium salt are as follows:
b1, putting fatty acid into a reaction kettle, and heating to 50-80 ℃;
b2, dropwise adding 10-15% sodium hydroxide solution in mass concentration into the reaction kettle, and measuring and controlling the pH value to be 6-7;
b3, keeping the temperature at 50-80 ℃ for 1-2h for full reaction;
b4, adding a cerium chloride solution into the reaction kettle, and controlling the temperature to be 50-70 ℃ and preserving the heat for 1-3h for full reaction;
b5, standing and layering for 1-3 h;
b6, separating an organic oil phase product in the reaction kettle;
b7, adding solvent oil into the water layer to extract oil phase products;
b8, combining the oil phase products obtained in the step B6 and the step B7 and carrying out vacuum drying treatment;
and B9, taking the product after vacuum drying to obtain the organic cerium salt.
5. The method for preparing an organic rare earth composite stabilizer according to claim 1, wherein the auxiliary agent is a lubricant.
6. The method for preparing an organic rare earth composite stabilizer according to claim 5, wherein the lubricant is any one of fatty acid, dicarboxylic acid ester, fatty acid ester, polyol fatty acid ester, high molecular weight composite ester, and silicone oil.
7. The method for preparing the organic rare earth composite stabilizer according to claim 1, wherein the phosphite is one or two of monobenzodiisooctyl phosphite, diphenylmonoisooctyl phosphite, triphenyl phosphite, triisodecyl phosphite and nonylphenol phosphite.
8. The method for preparing an organic rare earth composite stabilizer according to claim 1, wherein the epoxy compound is epoxidized soybean oil, epoxidized fatty acid, or epoxy ether.
9. The method for preparing the organic rare earth composite stabilizer according to claim 1, wherein the auxiliary heat stabilizer is one or more than two of beta diketones, fatty acid zinc and organic tin.
10. The method for preparing the organic rare earth composite stabilizer according to claim 1, comprising the steps of:
s1, putting one or two of organic cerium salt and organic lanthanum salt into a reaction kettle;
s2, putting the lubricant, the phosphite ester, the epoxy compound and the auxiliary heat stabilizer into a reaction kettle;
s3, fully stirring and mixing for 1-2 h;
s4, heating to 40-50 ℃ and reacting for 2-3 h;
and S5, fully mixing and reacting to obtain the stabilizer.
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| CN106893137A (en) * | 2017-03-27 | 2017-06-27 | 包头稀土研究院 | Polyalcohol rare earth complex heat stabilizer |
| CN107793674A (en) * | 2017-11-10 | 2018-03-13 | 内蒙古科技大学 | rare earth composite heat stabilizer for PVC and preparation method thereof |
| WO2020024309A1 (en) * | 2018-07-30 | 2020-02-06 | 深圳市志海实业股份有限公司 | Composite rare earth heat stablizer for pvc and preparation method therefor |
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| CN106893137A (en) * | 2017-03-27 | 2017-06-27 | 包头稀土研究院 | Polyalcohol rare earth complex heat stabilizer |
| CN107793674A (en) * | 2017-11-10 | 2018-03-13 | 内蒙古科技大学 | rare earth composite heat stabilizer for PVC and preparation method thereof |
| WO2020024309A1 (en) * | 2018-07-30 | 2020-02-06 | 深圳市志海实业股份有限公司 | Composite rare earth heat stablizer for pvc and preparation method therefor |
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