CN105504575A - Composite heat stabilizer for PVC (polyvinyl chloride) - Google Patents
Composite heat stabilizer for PVC (polyvinyl chloride) Download PDFInfo
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- CN105504575A CN105504575A CN201510883740.9A CN201510883740A CN105504575A CN 105504575 A CN105504575 A CN 105504575A CN 201510883740 A CN201510883740 A CN 201510883740A CN 105504575 A CN105504575 A CN 105504575A
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- 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
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- 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
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- 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
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a composite heat stabilizer for PVC (polyvinyl chloride). The composite heat stabilizer comprises components in parts by weight as follows: 0.6-3.0 parts of a compound shown in the formula I, 0-2.0 parts of calcium fatty acid, 0-2.0 parts of zinc fatty acid and 10-20 parts of a plasticizer. With the adoption of the composite heat stabilizer, compounds such as zinc chloride and the like can be prevented from being introduced into PVC products, and the initial dyeing property and the long-term heat stability of the hard PVC products are improved.
Description
Technical field
The present invention relates to a kind of composite thermal stabilizer, specifically a kind of composite thermal stabilizer for polyvinyl chloride.
Background technology
Polyvinyl chloride (PVC) resin is a kind of heat-sensitive substance, decomposing, therefore, in its hot procedure, usually needing to add thermo-stabilizer to prevent goods aging, variable color lower than having started during its processing temperature.
Compared to other thermo-stabilizer, calcium zinc system thermo-stabilizer, due to its nontoxic, safe advantage, is subject to extensive concern at present.For improving the effect of calcium zinc system thermo-stabilizer, selecting to add effective auxiliary heat stabilizer is method conventional at present.Beta-diketon is a kind of conventional organic auxiliary heat stabilizer, significantly can optimize the thermostable effect of calcium zinc system thermo-stabilizer, is all significantly improved to the initial coloring of PVC product and long-term ageing property.The ketone thermo-stabilizer developed at present is existing a lot.The Yan Xiaohong of Shanxi chemical research institute has synthesized stearoyl benzoyl methane, and develop composite thermal stabilizer T-386 with this, change the level (Yan Xiaohong that thermo-stabilizer effect reaches external trade mark RHdisastab50, the synthesis of PVC auxiliary heat stabilizer beta-diketon and application, modern plastics processed and applied, 2000,12 (3): 37-38); Nanjing University Chen Qiang has synthesized oleoyl benzoyl methane, this thermo-stabilizer and the composite heat-stable time of calcium zinc system agent reach more than 40min (Chen Qiang, Zhu Chunsheng, the synthesis of the nontoxic auxiliary heat stabilizer beta-diketon of PVC and application, modern plastics processed and applied, 1997,9 (1): 54-56); The week of Shandong Technology Univ is quick has synthesized 1,3-β-ketoglutaric acid ester compound, by composite with calcium zinc system thermo-stabilizer, heat-stable time reaches about 40min (Zhou Min, 1, the preparation and application of 3-β-ketoglutaric acid base PVC synergistic thermo-stabilizer, Shandong Technology Univ's master thesis); The Liu Qingbao of Beijing University of Chemical Technology has synthesized acetylacetone metallic compound, thermostable effect is up to 83min (Liu Qingbao, acetylacetone metallic compound synthesizes and studies the heat stabilization of PVC, Beijing University of Chemical Technology's master thesis).
Summary of the invention
The object of this invention is to provide a kind of composite thermal stabilizer simultaneously improving hard PVC goods initial stage form and aspect and long-term thermal stability.
For achieving the above object, the present invention by the following technical solutions:
For a composite thermal stabilizer for polyvinyl chloride, according to parts by weight, described composite thermal stabilizer comprises 0.6 ~ 3.0 part of formula I, 0 ~ 2.0 part of fatty acid calcium, 0 ~ 2.0 part of fatty acid zinc and 10 ~ 20 parts of softening agent.
Further, described fatty acid calcium is at least one in following compound: carbon atoms number is straight chain fatty acid group and the calcium salt that formed of calcium ion of 2 ~ 20.
Further, described fatty acid zinc is at least one in following compound: carbon atoms number is straight chain fatty acid group and the zinc salt that formed of zine ion of 2 ~ 20.
Further, described composite thermal stabilizer also comprises 0.2 ~ 2.0 part of additive.
Further, described additive is at least one in tetramethylolmethane, dipentaerythritol, tripentaerythritol, polyethylene wax, chlorinatedpolyethylene and stearic acid monoglycerides.
Further, described softening agent is at least one in dioctyl phthalate (DOP), dimixo-octyl phthalate, Di Iso Decyl Phthalate, diisononyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, sebacic acid two butyric acid, dioctyl sebacate, diisooctyl sebacate, two (2 Ethylbutanoic acid) triethylene Glycol ester, tributyl citrate, tributyl acetylcitrate and trioctyl trimellitate.
Further, the consisting of of described composite thermal stabilizer: 3.0 parts of formula I, 0.3 part of fatty acid calcium, 1.0 parts of fatty acid zincs, 15 parts of softening agent and 0.5 part of additive.
Further, described fatty acid calcium is calcium stearate, and described fatty acid zinc is Zinic stearas, and described additive is tetramethylolmethane and stearic acid monoglycerides.
The present invention has following beneficial effect:
The present invention adopts compound 3,3-(terephthaldehyde's base) two (pentanes-2,4-diketone) as organic auxiliary heat stabilizer, the composite thermal stabilizer of polyvinyl chloride is re-dubbed with fatty acid calcium, fatty acid zinc, deposit in case at appropriate softening agent, this composite thermal stabilizer can be avoided introducing the compounds such as zinc chloride in PVC product, improves initial coloring and the long-term thermal stability performance of hard PVC goods.Test result shows, this ketone thermo-stabilizer compared to other ketone thermo-stabilizers, form and aspect or long-term thermal stability aspect is all improved largely in the early stage.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further:
Embodiment 1
1 takes 3.0g3,3-(terephthaldehyde's base) two (pentane-2,4-diketone), 0.3g calcium stearate, 1.0g Zinic stearas, 0.2g tetramethylolmethane, 0.3g stearic acid monoglycerides;
More than 2 compositions and 15.0g dioctyl phthalate (DOP), 100.0gPVC resin (S-PVC, K value is 64) mixes;
3 double roller plastic-making devices said mixture being placed in roller temperature 170 DEG C, roll spacing 1mm are plasticated 5min, after getting sheet, be cut into the test piece of 2cm × 2cm square, PVC sheet is divided into groups to be placed in ageing oven in order, at 190 ± 1 DEG C, carry out oven ageing experiment test, take out test piece every 10min, observe the change of test piece colourity, time the results are shown in Table 1 till being continued until that test piece occurs that black is aging.
Comparative example stearoyl benzoyl methane substitutes 3,3-(terephthaldehyde's base) two (pentane-2,4-diketone), repeats above step.
Table 1
The composite thermal stabilizer of the contained I of the present invention is compared to stearoyl benzoyl methane, and form and aspect and long-term thermal stability aspect are all improved largely in the early stage.
Embodiment 2
1 takes 3.0g3,3-(terephthaldehyde's base) two (pentane-2,4-diketone), 0.3g calcium stearate, 1.0g Zinic stearas, 0.2g tetramethylolmethane, 0.3g stearic acid monoglycerides;
More than 2 compositions and 15.0g tributyl citrate, 100.0gPVC resin (S-PVC, K value is 64) mixes;
3 double roller plastic-making devices said mixture being placed in roller temperature 170 DEG C, roll spacing 1mm are plasticated 5min, after getting sheet, be cut into the test piece of 2cm × 2cm square, PVC sheet is divided into groups to be placed in ageing oven in order, at 190 ± 1 DEG C, carry out oven ageing experiment test, take out test piece every 10min, observe the change of test piece colourity, time the results are shown in Table 2 till being continued until that test piece occurs that black is aging.
Comparative example diphenylpropane-1,3-dione(DPPO) substitutes 3,3-(terephthaldehyde's base) two (pentane-2,4-diketone), repeats above step.
Table 2
The composite thermal stabilizer of the contained I of the present invention is compared to diphenylpropane-1,3-dione(DPPO), and form and aspect and long-term thermal stability aspect are all improved largely in the early stage.
Embodiment 3
1 takes 3.0g3,3-(terephthaldehyde's base) two (pentane-2,4-diketone), 0.3g calcium stearate, 1.0g Zinic stearas, 0.2g tetramethylolmethane, 0.3g stearic acid monoglycerides;
More than 2 compositions and 15.0g tributyl acetylcitrate, 100.0gPVC resin (S-PVC, K value is 64) mixes;
3 double roller plastic-making devices said mixture being placed in roller temperature 170 DEG C, roll spacing 1mm are plasticated 5min, after getting sheet, be cut into the test piece of 2cm × 2cm square, PVC sheet is divided into groups to be placed in ageing oven in order, at 190 ± 1 DEG C, carry out oven ageing experiment test, take out test piece every 10min, observe the change of test piece colourity, time the results are shown in Table 3 till being continued until that test piece occurs that black is aging.
Comparative example oenanthyl benzoyl methane substitutes 3,3-(terephthaldehyde's base) two (pentane-2,4-diketone), repeats above step.
Table 3
The composite thermal stabilizer of the contained I of the present invention is compared to oenanthyl benzoyl methane, and form and aspect and long-term thermal stability aspect are all improved largely in the early stage.
Embodiment 4
1 takes 3.0g3,3-(terephthaldehyde's base) two (pentane-2,4-diketone), 0.3g calcium stearate, 1.0g Zinic stearas, 0.2g tetramethylolmethane, 0.3g stearic acid monoglycerides;
More than 2 compositions and 15.0g trioctyl trimellitate, 100.0gPVC resin (S-PVC, K value is 64) mixes;
3 double roller plastic-making devices said mixture being placed in roller temperature 170 DEG C, roll spacing 1mm are plasticated 5min, after getting sheet, be cut into the test piece of 2cm × 2cm square, PVC sheet is divided into groups to be placed in ageing oven in order, at 190 ± 1 DEG C, carry out oven ageing experiment test, take out test piece every 10min, observe the change of test piece colourity, time the results are shown in Table 4 till being continued until that test piece occurs that black is aging.
Comparative example oleoyl benzoyl methane substitutes 3,3-(terephthaldehyde's base) two (pentane-2,4-diketone), repeats above step.
Table 4
The composite thermal stabilizer of the contained I of the present invention is compared to oleoyl benzoyl methane, and form and aspect and long-term thermal stability aspect are all improved largely in the early stage.
Embodiment 5
1 takes 3.0g3,3-(terephthaldehyde's base) two (pentane-2,4-diketone), 0.3g calcium stearate, 1.0g Zinic stearas, 0.2g tetramethylolmethane, 0.3g stearic acid monoglycerides;
More than 2 compositions and 15.0g dioctyl phthalate (DOP), 100.0gPVC resin (S-PVC, K value is 64) mixes;
3 double roller plastic-making devices said mixture being placed in roller temperature 170 DEG C, roll spacing 1mm are plasticated 5min, after getting sheet, be cut into the test piece of 2cm × 2cm square, PVC sheet is divided into groups to be placed in ageing oven in order, at 190 ± 1 DEG C, carry out oven ageing experiment test, take out test piece every 10min, observe the change of test piece colourity, time the results are shown in Table 5 till being continued until that test piece occurs that black is aging.
Comparative example 1,3-β-ketoglutaric acid substitutes 3,3-(terephthaldehyde's base) two (pentane-2,4-diketone), repeats above step.
Table 5
The composite thermal stabilizer of the contained I of the present invention is compared to 1,3-β-ketoglutaric acid, and form and aspect and long-term thermal stability aspect are all improved largely in the early stage.
Embodiment 6
1 takes 3.0g3,3-(terephthaldehyde's base) two (pentane-2,4-diketone), 0.3g calcium stearate, 1.0g Zinic stearas, 0.2g tetramethylolmethane, 0.3g stearic acid monoglycerides;
More than 2 compositions and 15.0g dioctyl sebacate, 100.0gPVC resin (S-PVC, K value is 64) mixes;
3 double roller plastic-making devices said mixture being placed in roller temperature 170 DEG C, roll spacing 1mm are plasticated 5min, after getting sheet, be cut into the test piece of 2cm × 2cm square, PVC sheet is divided into groups to be placed in ageing oven in order, at 190 ± 1 DEG C, carry out oven ageing experiment test, take out test piece every 10min, observe the change of test piece colourity, time the results are shown in Table 6 till being continued until that test piece occurs that black is aging.
Comparative example methyl ethyl diketone substitutes 3,3-(terephthaldehyde's base) two (pentane-2,4-diketone), repeats above step.
Table 6
The composite thermal stabilizer of the contained I of the present invention is compared to methyl ethyl diketone, and form and aspect and long-term thermal stability aspect are all improved largely in the early stage.
Embodiment 7
The composite thermal stabilizer of the present embodiment, comprise 0.6 part 3,3-(terephthaldehyde's base) two (pentane-2,4-diketone), 0.2 part of C8 ~ 10 straight chain fatty acid calcium, 0.5 part of C10 ~ 12 straight chain fatty acid zinc, 0.2 part of dipentaerythritol and 10 parts of dimixo-octyl phthalates.
Embodiment 8
The composite thermal stabilizer of the present embodiment, comprise 3.0 part 3,3-(terephthaldehyde's base) two (pentane-2,4-diketone), 2.0 parts of C6 ~ 10 straight chain fatty acid calcium, 2.0 parts of C8 ~ 12 straight chain fatty acid zinc, 2.0 parts of tripentaerythritols and 20 parts of Di Iso Decyl Phthalates.
Embodiment 9
The composite thermal stabilizer of the present embodiment, comprise 1.5 part 3,3-(terephthaldehyde's base) two (pentane-2,4-diketone), 1.0 parts of C2 ~ 6 straight chain fatty acid calcium, 1.5 parts of C16 ~ 20 straight chain fatty acid zinc, 1.5 parts of polyethylene waxs and 18 parts of diisononyl phthalate.
Embodiment 10
The composite thermal stabilizer of the present embodiment, comprise 2.5 part 3,3-(terephthaldehyde's base) two (pentane-2,4-diketone), 0.8 part of chlorinatedpolyethylene and 12 parts of dibutyl phthalates.
The above; be only the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, anyly belongs to those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (8)
1. for a composite thermal stabilizer for polyvinyl chloride, it is characterized in that, according to parts by weight, described composite thermal stabilizer comprises 0.6 ~ 3.0 part of formula I, 0 ~ 2.0 part of fatty acid calcium, 0 ~ 2.0 part of fatty acid zinc and 10 ~ 20 parts of softening agent.
2. composite thermal stabilizer according to claim 1, is characterized in that, described fatty acid calcium is at least one in following compound: carbon atoms number is straight chain fatty acid group and the calcium salt that formed of calcium ion of 2 ~ 20.
3. composite thermal stabilizer according to claim 1, is characterized in that, described fatty acid zinc is at least one in following compound: carbon atoms number is straight chain fatty acid group and the zinc salt that formed of zine ion of 2 ~ 20.
4. composite thermal stabilizer according to claim 1, is characterized in that, described composite thermal stabilizer also comprises 0.2 ~ 2.0 part of additive.
5. composite thermal stabilizer according to claim 4, is characterized in that, described additive is at least one in tetramethylolmethane, dipentaerythritol, tripentaerythritol, polyethylene wax, chlorinatedpolyethylene and stearic acid monoglycerides.
6. composite thermal stabilizer according to claim 1, it is characterized in that, described softening agent is at least one in dioctyl phthalate (DOP), dimixo-octyl phthalate, Di Iso Decyl Phthalate, diisononyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, sebacic acid two butyric acid, dioctyl sebacate, diisooctyl sebacate, two (2 Ethylbutanoic acid) triethylene Glycol ester, tributyl citrate, tributyl acetylcitrate and trioctyl trimellitate.
7. composite thermal stabilizer according to claim 1, is characterized in that, consisting of of described composite thermal stabilizer: 3.0 parts of formula I, 0.3 part of fatty acid calcium, 1.0 parts of fatty acid zincs, 15 parts of softening agent and 0.5 part of additive.
8. composite thermal stabilizer according to claim 7, is characterized in that, described fatty acid calcium is calcium stearate, and described fatty acid zinc is Zinic stearas, and described additive is tetramethylolmethane and stearic acid monoglycerides.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106700331A (en) * | 2016-12-13 | 2017-05-24 | 安庆市吉美装饰材料有限责任公司 | PVC (polyvinyl chloride) zinc-based heat stabilizer |
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| EP0947468A1 (en) * | 1996-10-16 | 1999-10-06 | Fuji Chemical Industry Co., Ltd. | Novel composite metal hydroxide salts, stabilizer for halogenoresins, and halogenoresin composition |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106700331A (en) * | 2016-12-13 | 2017-05-24 | 安庆市吉美装饰材料有限责任公司 | PVC (polyvinyl chloride) zinc-based heat stabilizer |
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