CN112812472B - Environment-friendly low-precipitation soft PVC material and preparation method thereof - Google Patents
Environment-friendly low-precipitation soft PVC material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000001556 precipitation Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 65
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 65
- 239000000843 powder Substances 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004014 plasticizer Substances 0.000 claims abstract description 21
- 239000003381 stabilizer Substances 0.000 claims abstract description 21
- 239000006084 composite stabilizer Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 239000000944 linseed oil Substances 0.000 claims description 22
- 235000021388 linseed oil Nutrition 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 17
- 239000004593 Epoxy Substances 0.000 claims description 12
- 239000003549 soybean oil Substances 0.000 claims description 12
- 235000012424 soybean oil Nutrition 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 159000000007 calcium salts Chemical class 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000003607 modifier Substances 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical group CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 5
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 5
- 239000008116 calcium stearate Substances 0.000 claims description 5
- 235000013539 calcium stearate Nutrition 0.000 claims description 5
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [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 5
- BJAJDJDODCWPNS-UHFFFAOYSA-N dotp Chemical group O=C1N2CCOC2=NC2=C1SC=C2 BJAJDJDODCWPNS-UHFFFAOYSA-N 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 5
- 229960001545 hydrotalcite Drugs 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical group [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 39
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 32
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 235000019253 formic acid Nutrition 0.000 description 8
- 239000008187 granular material Substances 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 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 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000006735 epoxidation reaction Methods 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- BKUSIKGSPSFQAC-RRKCRQDMSA-N 2'-deoxyinosine-5'-diphosphate Chemical compound O1[C@H](CO[P@@](O)(=O)OP(O)(O)=O)[C@@H](O)C[C@@H]1N1C(NC=NC2=O)=C2N=C1 BKUSIKGSPSFQAC-RRKCRQDMSA-N 0.000 description 3
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 3
- 102100035474 DNA polymerase kappa Human genes 0.000 description 3
- 101710108091 DNA polymerase kappa Proteins 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 3
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- SPBMMWPWMPIQPR-UHFFFAOYSA-L calcium;zinc;octadecanoate Chemical class [Ca+2].[Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O SPBMMWPWMPIQPR-UHFFFAOYSA-L 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000007551 Shore hardness test Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 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 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to an environment-friendly low-precipitation soft PVC material and a preparation method thereof, wherein 100 parts of polyvinyl chloride resin powder, 30-80 parts of environment-friendly plasticizer, 5-10 parts of auxiliary stabilizer, 0.1-0.5 part of calcium-zinc composite stabilizer and 0.2-0.6 part of wax powder are uniformly mixed at normal temperature to obtain the product. Adding polyvinyl chloride resin powder, an environment-friendly plasticizer and an auxiliary stabilizer into a high-speed hot kneader, mixing for 10-30min, adding a calcium-zinc composite stabilizer and wax powder, continuously mixing for 10-15min, discharging the kneaded material into a cold kneader, cooling, plasticizing, extruding, granulating and forming. Compared with the prior art, the PVC material obtained by the invention has the advantages of equal environmental protection, low precipitation, softness and high thermal stability.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an environment-friendly low-precipitation soft PVC material and a preparation method thereof.
Background
As the most widely used plastic raw material, polyvinyl chloride has been widely used in various industries both at home and abroad, and the use popularity of polyvinyl chloride products is very high at home and abroad, and the use rate of polyvinyl chloride products is also very high for people. In recent years, with the continuous improvement of the living standard of people, the environmental protection requirement of people on polyvinyl chloride plastic products is higher and higher, and especially in europe, the European Union passes the RoHS environmental protection instruction, and the use of o-benzene type plasticizers such as DEHP and the like in plastic products which directly affect the health of human bodies, such as toys for children, food packaging and the like, is specified.
The polyvinyl chloride products developed in the country before are basically the formula using the o-benzene plasticizing system, and can not meet the requirements of foreign merchants on environmental protection performance. Although the product is gradually improved, the quality of the product is different from that of the similar products in foreign countries, and the cost of the product is higher than that of the similar products in foreign countries, so that the popularization of the polyvinyl chloride product in China is seriously affected, and the similar products in China are more dependent on thousands of inlets. In order to meet the development requirements of the products, the low-precipitation transparent environment-friendly soft polyvinyl chloride granules which completely meet the requirements of European Union environmental protection instructions are developed by improving and perfecting the products on the basis of the existing raw materials, technological levels and equipment conditions.
Patent CN105778338A discloses an environment-friendly soft polyethylene pellet, the raw materials comprise: 100 parts of polyvinyl chloride resin; 30-130 parts of ester plasticizer; 5-10 parts of epoxidized soybean oil; 0.1-2 parts of calcium/zinc composite stabilizer; 0.1-1 part of lubricant; 0.01-0.5 parts of halloysite nanotube. The obtained soft polyvinyl chloride granules improve plasticizing efficiency, toughness and precipitation rate to a certain extent, but the precipitation rate of the product still cannot meet the requirements, and cannot meet the medical requirements.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an environment-friendly low-precipitation soft PVC material and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme: an environment-friendly low-precipitation soft PVC material comprises the following components in parts by weight:
100 parts of polyvinyl chloride resin powder
30-80 parts of environment-friendly plasticizer
5-10 parts of auxiliary stabilizer
0.1-0.5 part of calcium-zinc composite stabilizer
0.2 to 0.6 percent of wax powder.
The average polymerization degree of the polyvinyl chloride resin powder is 3000-5000.
The environment-friendly plasticizer is DOTP plasticizer. DOTP is colorless transparent oily liquid, the product is nontoxic and odorless safe plasticizer, has excellent heat resistance, cold resistance, light resistance and water resistance, does not contain harmful impurities such as phthalate (17P), heavy metal, polycyclic aromatic hydrocarbon and the like through SGS detection, is particularly suitable for being used in fields such as films, packaging films, toy films and the like, has good plasticizing effect, has no peculiar smell in the production process, has excellent cold resistance, heat resistance, extraction resistance and volatility, and has high accelerating rate. Exhibits excellent durability, soap water resistance and low temperature flexibility in the product.
The auxiliary stabilizer comprises epoxy linseed oil and epoxy soybean oil with the mass ratio of 50-80:50-20. The preparation method comprises the following steps: adding linseed oil and soybean oil into formic acid, stirring and mixing at 20-30 ℃ at the stirring speed of 800-1000 r/min, slowly adding hydrogen peroxide containing a catalyst, controlling the reaction temperature to be 50-70 ℃ and the stirring speed to be 1200-1500 r/min for epoxidation reaction, and continuing the reaction for 10-12 hours at the temperature of 50-70 ℃ after the hydrogen peroxide is added.
Further, the mass ratio of the linseed oil to the soybean oil to the formic acid is 50-80:50-20: 10 to 30 percent. The mass ratio of the catalyst to the hydrogen peroxide is 1:20-40; the mass ratio of the hydrogen peroxide to the linseed oil is 1-3:1. The catalyst is one or more of phosphoric acid, concentrated sulfuric acid, titanium dioxide and strong acid type cation exchange resin.
The calcium-zinc composite stabilizer is prepared by placing calcium salt, zinc salt, lubricant, antioxidant, dispersant and modifier into a stirrer to be stirred for 10-30 minutes. The calcium salt is calcium stearate with the particle size of 500-600 meshes, the zinc salt is zinc stearate with the particle size of 500-600 meshes, the lubricant is polyethylene wax, the dispersant is hydrotalcite with the particle size of 500-600 meshes, the antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester, and the modifier is epoxy resin. The mass ratio of the calcium salt to the zinc salt to the lubricant to the antioxidant to the dispersant to the modifier is 30-50:30-50:10-15:1-2:10-15:1-2; the stirring speed of the stirrer is 500-800 r/min.
The zinc stabilizer is compounded with calcium salt, zinc salt, lubricant, antioxidant, etc. as main components. It can replace lead-cadmium salts and organic tin and other toxic stabilizers, and has excellent heat stability, light stability, transparency and tinting strength. Practice proves that the PVC resin product has good processability, the thermal stabilization effect is equivalent to that of lead salt stabilizers, and the PVC resin product is a good nontoxic stabilizer.
(1) Can replace an organotin stabilizer and a lead salt stabilizer and meet the environmental protection and sanitation requirements of nontoxic wires and cables; (2) The product has excellent initial whiteness, thermal stability and sulfuration pollution resistance; (3) The composite material has good lubricity and unique coupling effect, endows the filler with good dispersibility, promotes the package with resin, improves the product performance, reduces the mechanical abrasion and prolongs the service life of equipment; (4) The plastic has the functions of toughening and promoting melting, and has good plasticizing fluidity; (5) The PVC mixture can be endowed with good uniform plasticization and high-speed melt fluidity, so that the surface of the product is smooth.
The wax powder is PE wax powder with the particle size of 10-100 microns.
The preparation method of the environment-friendly low-precipitation soft PVC material comprises the following steps: adding polyvinyl chloride resin powder, an environment-friendly plasticizer and an auxiliary stabilizer into a high-speed hot kneader, mixing for 10-30min, adding a calcium-zinc composite stabilizer and wax powder, continuously mixing for 10-15min, discharging the kneaded material into a cold kneader, cooling, plasticizing, extruding, granulating and forming.
The temperature of the high-speed thermal kneader is 60-125 ℃, and the rotating speed is 500-800 r/min;
the temperature of the cold kneader is 0-25 ℃, and the rotating speed is 500-800 r/min.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, linseed oil and a small amount of soybean oil are used as raw materials, and the epoxy linseed oil is prepared as an auxiliary agent for interaction, so that on one hand, the epoxy value is improved and can reach 8.9, wherein the epoxy group can trap free radical Cl < - > separated from degradation of polyvinyl chloride, terminate free radical reaction of degradation of polyvinyl chloride, slow down degradation speed, remarkably improve light resistance, heat resistance and oil resistance of a polyvinyl chloride product, and can endow the product with good mechanical strength, weather resistance and electrical property. The PVC resin has plasticizing effect on PVC, can stabilize active chlorine atoms on PVC chains, and can quickly absorb HCl degraded by heat and light, so that continuous decomposition of PVC is retarded, and stabilizing effect is achieved. On the other hand, the epoxy linseed oil obtained by the method can be synergistically acted with environment-friendly plasticizer DOTP to react with polyvinyl chloride resin powder, the breaking elongation and impact strength of the obtained PVC material are improved by 30%, the mechanical property of the PVC material is enhanced, the flexibility of the PVC material is also improved, the hardness is reduced, and the PVC material is easier to prepare a medical transfusion (blood) tube with good flexibility, tensile resistance, tearing resistance and low separation rate.
2. The calcium zinc heat stabilizer is prepared by adopting a special method, when the calcium zinc heat stabilizer is acted on PVC resin together with the plasticizer DOTP, the epoxy linseed oil and the wax powder, the uniform dispersibility of each component in the PVC resin powder can be improved, the properties of various raw materials are stimulated, and the obtained product is not easy to change color and has excellent heat stability.
3. The product is an environment-friendly product, passes SGS detection, accords with EU RoHS environment-friendly instruction, has DEHP, DINP, DBP, DIDP, DNOP and BBP content of thousands of 0.003 percent, and can be used for products exported from EU, such as toys for children, food packaging and the like.
4. The content of toxic heavy metals such as lead, pickaxe, picking and the like in the product is 2mg/kg, and the content of polycyclic aromatic hydrocarbon PAHs is 0.lmg/kg.
5. Compared with the existing soft polyvinyl chloride granules in China, the polyvinyl chloride granules have extremely low plasticizer precipitation, and compared with the existing DOP plasticizing system polyvinyl chloride granules in China, the polyvinyl chloride granules have the precipitation reduced by more than 1/4, and have stronger protection and safety on environment and human health.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The preparation of the environment-friendly low-precipitation soft PVC material comprises the following steps:
(1) Preparation of auxiliary stabilizer: adding linseed oil and soybean oil into formic acid, stirring and mixing at 25 ℃, slowly adding hydrogen peroxide containing a catalyst at the stirring speed of 9000r/min, controlling the reaction temperature to be 60 ℃, and performing epoxidation reaction at the stirring speed of 1300r/min, and after the hydrogen peroxide is added, keeping the temperature at 60 ℃ and continuing the reaction for 11 hours. The mass ratio of the linseed oil to the soybean oil to the formic acid is 60:40:20. the mass ratio of the catalyst to the hydrogen peroxide is 1:30; the mass ratio of the hydrogen peroxide to the linseed oil is 2:1. The catalyst is phosphoric acid.
(2) Preparation of a calcium-zinc composite stabilizer: placing calcium stearate, zinc stearate, polyethylene wax, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester, hydrotalcite and epoxy resin in a mass ratio of 40:40:12:1.5:12:1.5 into a stirrer, and stirring for 20 minutes at 600r/min to obtain the modified calcium stearate-zinc stearate composite material;
(3) The preparation of the environment-friendly low-precipitation soft PVC material comprises the steps of adding polyvinyl chloride resin powder, an environment-friendly plasticizer and an auxiliary stabilizer into a high-speed hot kneader, mixing for 20min at the temperature of 100 ℃ at the rotating speed of 600r/min, adding a calcium-zinc composite stabilizer and wax powder into the high-speed hot kneader, mixing for 12min at the temperature of 10 ℃ at the rotating speed of 600r/min, discharging the kneaded material into the cold kneader, cooling, plasticizing, extruding and granulating, and forming.
Examples 1 to 10
The parts by weight of the raw materials used in each example are shown in table 1 below:
TABLE 1 the amounts of the components in kg
Comparative example 1
The epoxy linseed oil and the calcium zinc composite stabilizer are all commercial products, and the rest is the same as in example 7.
2. The experimental method comprises the following steps:
GB/T1040 plastic tensile property test method
GB 2411 plastic Shore hardness test method
Congo red method and PH method for GB/T2917 polyvinyl chloride thermal stability test method
GB 1033 plastic relative density test method
Program for measuring content of limiting substances in IEC 62321 Ed 111/54/CDV electronic and electric products
3. Product requirements
3.1 appearance: the external dimension is generally round granular material with the diameter of 3.0-4.0 mm and the length of 2.5-3.Smm. Other shapes of particles of comparable size and uniformity are also possible.
3.2 appearance: the appearance is transparent granular matters, the plasticizing is uniform, and the resin and foreign matters which are not plasticized are avoided.
3.3 physical and mechanical properties of the environmentally friendly low-precipitation soft polyvinyl chloride granules are shown in Table 2
TABLE 2
The product prepared by the method disclosed by the invention is subjected to SGS detection, accords with the EU RoHS environment-friendly instruction, has DEHP, DINP, DBP, DIDP, DNOP and BBP contents less than 0.003% and can be used for products exported from EU, such as toys for children, food packages and the like.
The content of toxic heavy metals such as lead, pick and mining in the product is less than 2mg/kg, and the content of polycyclic aromatic hydrocarbon PAHs is 0.lmg/kg.
Example 11
The preparation of the environment-friendly low-precipitation soft PVC material comprises the following steps:
(1) Preparation of auxiliary stabilizer: adding linseed oil and soybean oil into formic acid, stirring and mixing at 20 ℃, slowly adding hydrogen peroxide containing a catalyst at the stirring speed of 800r/min, controlling the reaction temperature to be 50 ℃, and performing epoxidation reaction at the stirring speed of 1200r/min, and after the hydrogen peroxide is added, keeping the temperature at 50 ℃ and continuing the reaction for 10 hours. The mass ratio of the linseed oil to the soybean oil to the formic acid is 50:50:10. the mass ratio of the catalyst to the hydrogen peroxide is 1:20; the mass ratio of the hydrogen peroxide to the linseed oil is 1:1. The catalyst is titanium dioxide.
(2) Preparation of a calcium-zinc composite stabilizer: placing calcium stearate, zinc stearate, polyethylene wax, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester, hydrotalcite and epoxy resin in a mass ratio of 30:30:10:1:10:1 into a stirrer, and stirring for 30 minutes at 500r/min to obtain the composite material
(3) The preparation of the environment-friendly low-precipitation soft PVC material comprises the steps of weighing 100 parts of polyvinyl chloride resin powder, 30 parts of environment-friendly plasticizer, 5 parts of epoxy linseed oil, 0.1 part of calcium-zinc composite stabilizer and 0.2 part of wax powder according to parts by weight, adding the polyvinyl chloride resin powder, the environment-friendly plasticizer and the auxiliary stabilizer into a high-speed hot kneader, mixing for 30min at the temperature of 60 ℃ at the rotating speed of 500r/min, adding the calcium-zinc composite stabilizer and the wax powder at the temperature of 0 ℃ at the rotating speed of 500r/min, continuously mixing for 15min, discharging the kneaded material into the cold kneader, cooling, plasticizing, extruding and granulating, and forming.
Comparative example 2
The calcium zinc composite stabilizer is a commercial product, and the rest is the same as in example 11.
Example 12
The preparation of the environment-friendly low-precipitation soft PVC material comprises the following steps:
(1) Preparation of auxiliary stabilizer: adding linseed oil and soybean oil into formic acid, stirring and mixing at 30 ℃, slowly adding hydrogen peroxide containing a catalyst at the stirring speed of 1000r/min, controlling the reaction temperature to be 70 ℃ and the stirring speed to be 1500r/min for epoxidation, and continuing the reaction for 12 hours after the hydrogen peroxide is added, and keeping the temperature at 70 ℃. The mass ratio of the linseed oil to the soybean oil to the formic acid is 80:20:30. the mass ratio of the catalyst to the hydrogen peroxide is 1:40; the mass ratio of the hydrogen peroxide to the linseed oil is 1:1. The catalyst is one or more of phosphoric acid, concentrated sulfuric acid, titanium dioxide and strong acid type cation exchange resin.
(2) Preparation of a calcium-zinc composite stabilizer: placing calcium stearate, zinc stearate, polyethylene wax, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester, hydrotalcite and epoxy resin in a mass ratio of 50:50:15:2:15:2 into a stirrer, and stirring for 10 minutes at 800r/min to obtain the modified calcium stearate-zinc stearate composite material
(3) The preparation of the environment-friendly low-precipitation soft PVC material comprises the steps of weighing 100 parts of polyvinyl chloride resin powder, 80 parts of environment-friendly plasticizer, 10 parts of epoxy linseed oil, 0.5 part of calcium-zinc composite stabilizer and 0.6 part of wax powder according to parts by weight, adding the polyvinyl chloride resin powder, the environment-friendly plasticizer and the auxiliary stabilizer into a high-speed hot kneader, mixing for 10min at the temperature of 125 ℃ at the rotating speed of 800r/min, adding the calcium-zinc composite stabilizer and the wax powder at the temperature of 25 ℃ at the rotating speed of 800r/min, continuously mixing for 10min, discharging the kneaded material into the cold kneader, cooling, plasticizing, extruding and granulating, and forming.
Comparative example 3
The auxiliary stabilizer is commercially available epoxy linseed oil, the calcium-zinc composite stabilizer is commercially available product, and the rest is the same as in example 12.
TABLE 3 Table 3
| Examples | Example 11 | Comparative example 2 | Example 12 | Comparative example 3 |
| Hardness (Shore A) | 77 | 75 | 68 | 66 |
| Tensile strength, mpa is more than or equal to | 18.8 | 7.8 | 18.5 | 6.5 |
| Elongation at break,% > or more | 379 | 235 | 376 | 203 |
| The heat stability time at 180 ℃ is more than or equal to min | 156 | 73 | 168 | 70 |
| Separation rate% | 0.05 | 0.95 | 0.05 | 0.98 |
The obtained product passes SGS detection, accords with European Union RoHS environmental protection instruction, has DEHP, DINP, DBP, DIDP, DNOP and BBP content less than 0.003 percent, and can be used for products exported from European Union, such as toys for children, food packaging and the like.
The content of toxic heavy metals such as lead, pick and mining in the product is less than 2mg/kg, and the content of polycyclic aromatic hydrocarbon PAHs is 0.lmg/kg.
Claims (7)
1. The environment-friendly low-precipitation soft PVC material is characterized by comprising the following components in parts by weight:
100 parts of polyvinyl chloride resin powder
30-80 parts of environment-friendly plasticizer
5-10 parts of auxiliary stabilizer
0.1-0.5 part of calcium-zinc composite stabilizer
0.2 to 0.6 percent of wax powder;
the auxiliary stabilizer comprises epoxy linseed oil and epoxy soybean oil in a mass ratio of 50-80:50-20;
the calcium-zinc composite stabilizer is prepared by placing calcium salt, zinc salt, lubricant, antioxidant, dispersant and modifier into a stirrer to be stirred for 10-30 minutes; the calcium salt is calcium stearate with the particle size of 500-600 meshes, the zinc salt is zinc stearate with the particle size of 500-600 meshes, the lubricant is polyethylene wax, the dispersant is hydrotalcite with the particle size of 500-600 meshes, the antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester, and the modifier is epoxy resin; the mass ratio of the calcium salt to the zinc salt to the lubricant to the antioxidant to the dispersant to the modifier is 30-50:30-50:10-15:1-2:10-15:1-2.
2. The environment-friendly low-precipitation soft PVC material according to claim 1, wherein the average polymerization degree of the polyvinyl chloride resin powder is 3000-5000.
3. The environment-friendly low-precipitation soft PVC material according to claim 1, wherein the environment-friendly plasticizer is DOTP plasticizer.
4. The environment-friendly low-precipitation soft PVC material according to claim 1, wherein the stirring speed of the stirrer is 500-800 r/min.
5. The environment-friendly low-precipitation soft PVC material according to claim 1, wherein the wax powder is PE wax powder with the particle size of 10-100 microns.
6. The method for preparing the environment-friendly low-precipitation soft PVC material as claimed in claim 1, which is characterized by comprising the following steps: adding polyvinyl chloride resin powder, an environment-friendly plasticizer and an auxiliary stabilizer into a high-speed hot kneader, mixing for 10-30min, adding a calcium-zinc composite stabilizer and wax powder, continuously mixing for 10-15min, discharging the kneaded material into a cold kneader, cooling, plasticizing, extruding, granulating and forming.
7. The method for preparing the environment-friendly low-precipitation soft PVC material according to claim 6, wherein the temperature of the high-speed hot kneader is 60-125 ℃ and the rotating speed is 500-800 r/min;
the temperature of the cold kneader is 0-25 ℃, and the rotating speed is 500-800 r/min.
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