CN112852070A - Calcium zinc stabilizer with better colorability and thermal stability - Google Patents
Calcium zinc stabilizer with better colorability and thermal stability Download PDFInfo
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- CN112852070A CN112852070A CN202110080610.7A CN202110080610A CN112852070A CN 112852070 A CN112852070 A CN 112852070A CN 202110080610 A CN202110080610 A CN 202110080610A CN 112852070 A CN112852070 A CN 112852070A
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- parts
- zinc
- thermal stability
- stabilizer
- calcium
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- 239000003381 stabilizer Substances 0.000 title claims abstract description 38
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000000314 lubricant Substances 0.000 claims abstract description 24
- 108010073771 Soybean Proteins Proteins 0.000 claims abstract description 20
- 235000019710 soybean protein Nutrition 0.000 claims abstract description 20
- 150000003751 zinc Chemical class 0.000 claims abstract description 19
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 17
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 16
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 16
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 16
- 238000004040 coloring Methods 0.000 claims abstract description 15
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000008116 calcium stearate Substances 0.000 claims abstract description 13
- 235000013539 calcium stearate Nutrition 0.000 claims abstract description 13
- 239000002530 phenolic antioxidant Substances 0.000 claims abstract description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 12
- 239000000194 fatty acid Substances 0.000 claims description 12
- 229930195729 fatty acid Natural products 0.000 claims description 12
- 150000004665 fatty acids Chemical class 0.000 claims description 12
- -1 salt compound Chemical class 0.000 claims description 12
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- LRQGFQDEQPZDQC-UHFFFAOYSA-N 1-Phenyl-1,3-eicosanedione Chemical compound CCCCCCCCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 LRQGFQDEQPZDQC-UHFFFAOYSA-N 0.000 claims description 8
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 7
- 239000012188 paraffin wax Substances 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000004611 light stabiliser Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 239000001993 wax Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- RYOLIMKPFQALMC-UHFFFAOYSA-L zinc;4-methylbenzoate Chemical compound [Zn+2].CC1=CC=C(C([O-])=O)C=C1.CC1=CC=C(C([O-])=O)C=C1 RYOLIMKPFQALMC-UHFFFAOYSA-L 0.000 claims description 3
- LYSLZRDZOBAUFL-UHFFFAOYSA-L zinc;4-tert-butylbenzoate Chemical compound [Zn+2].CC(C)(C)C1=CC=C(C([O-])=O)C=C1.CC(C)(C)C1=CC=C(C([O-])=O)C=C1 LYSLZRDZOBAUFL-UHFFFAOYSA-L 0.000 claims description 3
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 abstract description 4
- 238000001746 injection moulding Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 238000005204 segregation Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 150000008431 aliphatic amides Chemical class 0.000 description 4
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 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 3
- 230000007774 longterm Effects 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 3
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 229940116335 lauramide Drugs 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 229940037312 stearamide Drugs 0.000 description 2
- 239000004593 Epoxy Chemical class 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 238000004383 yellowing 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Landscapes
- 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 discloses a calcium zinc stabilizer with better colorability and thermal stability, which comprises the following components in parts by weight: 30-50 parts of zinc salt of aromatic carboxylic acid, 25-45 parts of calcium stearate, 15-20 parts of hydrotalcite, 0.2-1 part of thermal stability promoter, 0.1-1 part of coloring stabilizer, 2-7 parts of lubricant, 1-5 parts of modified soybean protein isolate and 3-7 parts of phenolic antioxidant. The calcium zinc stabilizer with good colorability and thermal stability has good colorability and thermal stability, and can be well used for PVC extrusion and processing in the injection molding industry.
Description
The technical field is as follows:
the invention relates to the field of plastic stabilizers, in particular to a calcium-zinc stabilizer with better colorability resistance and thermal stability.
Background art:
since vinyl chloride resins are not only excellent in flame retardancy, chemical resistance, mechanical stability, transparency, adhesion, printability, etc., but also can be easily modified from hard to soft in hardness by adding a plasticizer, vinyl chloride resins are used in various applications. In particular, a hard vinyl chloride resin composition completely free of a plasticizer and a semi-hard vinyl chloride resin composition containing a small amount of a plasticizer have excellent rigidity, and thus are widely used for building materials and the like. Therefore, such vinyl chloride resin compositions are required to exhibit higher levels of properties not only during the treatment of exposure to high temperature and high pressure but also as molded articles in terms of thermal stability, resistance to coloration, resistance to thermal coloration, weather resistance, and the like. In addition, for hard transparent molded articles, vinyl chloride resins are also used as extremely general-purpose resins requiring glass-like transparency in containers, industrial sheets, decorative sheets, films, sheets and the like. On the other hand, vinyl chloride resins are known to have disadvantages in that they are not sufficiently stable to light and heat, and when they are heat molded or used as products, they may be degraded mainly by dehydrohalogenation.
In order to meet these performance requirements and overcome the disadvantages, it has been conventionally proposed to improve the stability of a vinyl chloride resin by adding various stabilizers such as organic acid metal salts, organic tin compounds, organic phosphite compounds and epoxy compounds, an antioxidant and an ultraviolet absorber.
However, even in vinyl chloride resin compositions containing such stabilizers, when they are thermally molded or used as products, degradation due to the reduction in molecular weight and dehydrohalogenation of the vinyl chloride resins thereof is not completely suppressed. In addition, there is a problem that the vinyl chloride resin composition is colored due to the decrease in molecular weight of the vinyl chloride resin thereof or the generation of hydrogen chloride.
The invention content is as follows:
the invention aims to solve the technical problem of providing a calcium zinc stabilizer with better coloring resistance and thermal stability, and the calcium zinc stabilizer with better coloring resistance and thermal stability has better coloring resistance and thermal stability when being combined with polyethylene resin, so that the polyethylene resin has wider application, and can be well used for processing in PVC extrusion and injection molding industries.
The technical scheme of the invention is to provide a calcium zinc stabilizer with better colorability and thermal stability, which comprises the following components in parts by weight: 30-50 parts of zinc salt of aromatic carboxylic acid, 25-45 parts of calcium stearate, 15-20 parts of hydrotalcite, 0.2-1 part of thermal stability promoter, 0.1-1 part of coloring stabilizer, 2-7 parts of lubricant, 1-5 parts of modified soybean protein isolate and 3-7 parts of phenolic antioxidant, wherein the thermal stability promoter is one or the combination of stearoylbenzoylmethane and zinc acetylacetonate.
As a preferable technical scheme, the zinc salt of the aromatic carboxylic acid is any one or combination of zinc benzoate, zinc toluate and zinc 4-tert-butylbenzoate.
As a preferred technical solution, the hydrotalcite is a composite salt compound formed by magnesium and aluminum or zinc, magnesium and aluminum.
As a preferable technical scheme, the coloring stabilizer is a hindered amine light stabilizer or nano titanium dioxide.
As a preferred technical scheme, the modified soybean protein isolate is prepared by modifying the soybean protein isolate by using a sodium hydroxide, sodium dodecyl benzene sulfonate and urea composite modifier.
Preferably, the lubricant is a hydrocarbon-based lubricant, a fatty acid-based lubricant, or a fatty acid amide-based lubricant. Hydrocarbon-based lubricants such as paraffin wax, polyethylene wax, chlorinated hydrocarbons, and fluorocarbons; fatty acid-based lubricants such as higher fatty acids (e.g., lauric acid, and sebacic acid) and oxygen-containing fatty acids (e.g., hydroxystearic acid); aliphatic amide-based lubricants, such as aliphatic amide compounds (e.g., stearamide, lauramide, and oleamide) and alkylenebis aliphatic amides (e.g., methylenebisstearamide and ethylenebisstearamide).
The preferable technical scheme is that the composition comprises the following components in parts by weight: 35 parts of zinc salt of aromatic carboxylic acid, 25 parts of calcium stearate, 17 parts of hydrotalcite, 0.5 part of zinc acetylacetonate, 0.3 part of hindered amine light stabilizer, 2 parts of polyethylene wax, 2 parts of modified soybean protein isolate and 3 parts of phenolic antioxidant.
Further, the paint comprises the following components in parts by weight: 38 parts of zinc salt of aromatic carboxylic acid, 27 parts of calcium stearate, 18 parts of hydrotalcite, 0.5 part of stearoylbenzoylmethane, 0.5 part of nano titanium dioxide, 3 parts of paraffin, 2 parts of modified soybean protein isolate and 3 parts of phenolic antioxidant.
Compared with the prior art, the invention has the following advantages after adopting the scheme: zinc stearate in the traditional formula is replaced by zinc salt of aromatic carboxylic acid, so that the zinc salt can be better applied to transparent products, and has more stable color maintenance for products with other colors; the thermal stability promoter can effectively promote thermal stability, the coloring stabilizer is beneficial to improving coloring resistance, and resin segregation phenomenon easily caused by other modifiers can be reduced by modifying the soybean protein isolate. In addition, the heat stabilizer is one or the combination of stearoylbenzoylmethane and zinc acetylacetonate, which is helpful for capturing HCL by matching with calcium and zinc to form long-term effect of weather resistance stability.
The specific implementation mode is as follows:
the invention is further illustrated with respect to specific embodiments below:
a calcium zinc stabilizer with better colorability and thermal stability comprises the following components in parts by weight: 30-50 parts of zinc salt of aromatic carboxylic acid, 25-45 parts of calcium stearate, 15-20 parts of hydrotalcite, 0.2-1 part of thermal stability promoter, 0.1-1 part of coloring stabilizer, 2-7 parts of lubricant, 1-5 parts of modified soybean protein isolate and 3-7 parts of phenolic antioxidant, wherein the thermal stability promoter is one or the combination of stearoylbenzoylmethane and zinc acetylacetonate.
Among them, the zinc salt of the aromatic carboxylic acid is preferably any one or a combination of zinc benzoate, zinc toluate or zinc 4-tert-butylbenzoate, and the hydrotalcite is a composite salt compound formed by magnesium and aluminum or zinc, magnesium and aluminum; the coloring stabilizer is hindered amine light stabilizer or nano titanium dioxide; the lubricant is a hydrocarbon-based lubricant, a fatty acid-based lubricant, or a fatty acid amide-based lubricant. Hydrocarbon-based lubricants such as paraffin wax, polyethylene wax, chlorinated hydrocarbons, and fluorocarbons; fatty acid-based lubricants such as higher fatty acids (e.g., lauric acid, and sebacic acid) and oxygen-containing fatty acids (e.g., hydroxystearic acid); aliphatic amide-based lubricants, such as aliphatic amide compounds (e.g., stearamide, lauramide, and oleamide) and alkylenebis aliphatic amides (e.g., methylenebisstearamide and ethylenebisstearamide).
Furthermore, the modified soybean protein isolate is formed by modifying the soybean protein isolate through a sodium hydroxide, sodium dodecyl benzene sulfonate and urea composite modifier, so that the resin segregation phenomenon easily caused by other modifiers can be reduced.
The different examples were analyzed with respect to their properties of heat stability and resistance to staining as follows:
example 1
A calcium zinc stabilizer with better colorability and thermal stability comprises the following components in parts by weight: 35 parts of zinc salt of aromatic carboxylic acid, 25 parts of calcium stearate, 17 parts of hydrotalcite, 0.5 part of zinc acetylacetonate, 0.3 part of hindered amine light stabilizer, 2 parts of polyethylene wax, 2 parts of modified soybean protein isolate and 3 parts of phenolic antioxidant.
Example 2
A calcium zinc stabilizer with better colorability and thermal stability comprises the following components in parts by weight: 38 parts of zinc salt of aromatic carboxylic acid, 27 parts of calcium stearate, 18 parts of hydrotalcite, 0.5 part of stearoylbenzoylmethane, 0.5 part of nano titanium dioxide, 3 parts of paraffin, 2 parts of modified soybean protein isolate and 3 parts of phenolic antioxidant.
Example 3
A calcium zinc stabilizer with better colorability and thermal stability comprises the following components in parts by weight: 38 parts of zinc salt of aromatic carboxylic acid, 28 parts of calcium stearate, 15 parts of hydrotalcite, 0.5 part of zinc acetylacetonate, 0.6 part of nano titanium dioxide, 2 parts of paraffin, 2 parts of modified soybean protein isolate and 3 parts of phenolic antioxidant.
Evaluation of Properties
The calcium zinc stabilizer of the comparative example consists of the following components in parts by weight: 38 parts of zinc stearate, 28 parts of calcium stearate, 15 parts of hydrotalcite, 0.5 part of lubricant, 2 parts of modifier and 3 parts of antioxidant.
PVC materials are prepared from the calcium zinc stabilizer of the examples and the comparative examples according to the following mixing ratio, by mass, 100 parts of PVC, 70 parts of calcium carbonate, 15 parts of wood powder, 6 parts of calcium zinc stabilizer, 1 part of foaming agent, 0.5 part of cross-linking agent and 2 parts of lubricating agent. The discoloration time and long-term stability of the PVC materials prepared using examples 1-3 and comparative example 1 were examined by congo red method and hot oven method, respectively.
The test method is as follows:
congo red method, implementing standard GB/T2917-2002. The PVC material obtained in examples 1 to 3 and comparative example was cut into squares having a side length of 2mm, and the squares were placed in a reaction tube having a height of about 50mm, and the reaction tube was slightly vibrated without making the sample excessively solid or stuck to the wall of the tube. The congo red test paper was placed two centimeters above the sample pellet and the stopper was plugged. The test tube was then placed in an oil bath at the temperature required for the particular test, and the time taken for the test strip to change from red to blue was observed and recorded, the result corresponding to the initial coloration.
Thermal oven method, the PVC materials prepared using examples 1-3 and comparative example 1 were placed in a thermal oven and the color was observed after heating for 150 min.
The results are shown in Table 1.
TABLE 1
| Detecting items | Example 1 | Example 2 | Example 3 | Comparative example |
| Time to change color (min) | 157 | 162 | 159 | 96 |
| Stability of | Does not change color | Does not change color | Does not change color | Yellowing of |
Therefore, compared with the calcium zinc stabilizer in the prior art, the calcium zinc stabilizer provided by the invention is suitable for PVC resin, and has better thermal stability and coloring resistance. And in the test, the control example is found to have a certain segregation phenomenon, while the examples 1 to 3 have no segregation phenomenon.
The zinc salt of the aromatic carboxylic acid is used for replacing zinc stearate in the traditional formula, so that the zinc salt can be better applied to transparent products, and has more stable color maintenance for products with other colors; the thermal stability promoter can effectively promote thermal stability, the coloring stabilizer is beneficial to improving coloring resistance, and resin segregation phenomenon easily caused by other modifiers can be reduced by modifying the soybean protein isolate. In addition, the heat stabilizer is one or the combination of stearoylbenzoylmethane and zinc acetylacetonate, which is helpful for capturing HCL by matching with calcium and zinc to form long-term effect of weather resistance stability. The PVC extrusion die can be well used for processing in PVC extrusion and injection molding industries.
The foregoing is illustrative of the preferred embodiments of the present invention only and is not to be construed as limiting the claims. All the equivalent structures or equivalent process changes made by the description of the invention are included in the scope of the patent protection of the invention.
Claims (9)
1. A calcium zinc stabilizer with better colorability and thermal stability is characterized in that: the composition comprises the following components in parts by weight: 30-50 parts of zinc salt of aromatic carboxylic acid, 25-45 parts of calcium stearate, 15-20 parts of hydrotalcite, 0.2-1 part of thermal stability promoter, 0.1-1 part of coloring stabilizer, 2-7 parts of lubricant, 1-5 parts of modified soybean protein isolate and 3-7 parts of phenolic antioxidant, wherein the thermal stability promoter is one or the combination of stearoylbenzoylmethane and zinc acetylacetonate.
2. The calcium zinc stabilizer with better stain resistance and thermal stability of claim 1, wherein: the zinc salt of the aromatic carboxylic acid is any one or combination of zinc benzoate, zinc toluate or zinc 4-tert-butylbenzoate.
3. The calcium zinc stabilizer with better stain resistance and thermal stability of claim 1, wherein: hydrotalcite is a complex salt compound formed from magnesium and aluminum or zinc, magnesium and aluminum.
4. The calcium zinc stabilizer with better stain resistance and thermal stability of claim 1, wherein: the coloring stabilizer is hindered amine light stabilizer or nano titanium dioxide.
5. The calcium zinc stabilizer with better stain resistance and thermal stability of claim 1, wherein: the modified soybean protein isolate is prepared by modifying the soybean protein isolate by using a sodium hydroxide, sodium dodecyl benzene sulfonate and urea composite modifier.
6. The calcium zinc stabilizer with better stain resistance and thermal stability of claim 1, wherein: the lubricant is any one of a hydrocarbon-based lubricant, a fatty acid-based lubricant, and a fatty acid amide-based lubricant.
7. The calcium zinc stabilizer with better stain resistance and thermal stability of claim 1, wherein: the composition comprises the following components in parts by weight: 35 parts of zinc salt of aromatic carboxylic acid, 25 parts of calcium stearate, 17 parts of hydrotalcite, 0.5 part of zinc acetylacetonate, 0.3 part of hindered amine light stabilizer, 2 parts of polyethylene wax, 2 parts of modified soybean protein isolate and 3 parts of phenolic antioxidant.
8. The calcium zinc stabilizer with better stain resistance and thermal stability of claim 1, wherein: the composition comprises the following components in parts by weight: 38 parts of zinc salt of aromatic carboxylic acid, 27 parts of calcium stearate, 18 parts of hydrotalcite, 0.5 part of stearoylbenzoylmethane, 0.5 part of nano titanium dioxide, 3 parts of paraffin, 2 parts of modified soybean protein isolate and 3 parts of phenolic antioxidant.
9. The calcium zinc stabilizer with better stain resistance and thermal stability of claim 1, wherein: the composition consists of the following components: 38 parts of zinc salt of aromatic carboxylic acid, 28 parts of calcium stearate, 15 parts of hydrotalcite, 0.5 part of zinc acetylacetonate, 0.6 part of nano titanium dioxide, 2 parts of paraffin, 2 parts of modified soybean protein isolate and 3 parts of phenolic antioxidant.
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