CN110452445A - A kind of sheet calcium-zinc composite stabilizing agent and its technological process of production - Google Patents
A kind of sheet calcium-zinc composite stabilizing agent and its technological process of production Download PDFInfo
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Abstract
The invention discloses a kind of sheet calcium-zinc composite stabilizing agent and its technological process of productions, comprising the following steps: the preparation of calcium stearate, the preparation of cis- -1,2- cyclohexane cyclohexanedimethanodibasic, two mannitol ester group zinc metal alkoxide, the preparation of sheet calcium-zinc composite stabilizing agent.Raw material of the PVC with calcium-zinc composite stabilizing agent comprising following parts by weight of component: 10-30 parts of calcium stearate, two 10-30 parts of mannitol ester group zinc metal alkoxide of cis- -1,2- cyclohexane cyclohexanedimethanodibasic, 10-15 parts of auxiliary stabilizer, 5-10 parts of zeolite, 10-20 parts of lubricant, 1-5 parts of antioxidant.The present invention is with calcium stearate and cis- -1, two mannitol ester group zinc metal alkoxide of 2- cyclohexane cyclohexanedimethanodibasic is main stabilizer, compared with some novel environment-friendly heat stabilizers such as zinc stearate, cis- -1, two mannitol ester group zinc metal alkoxide of 2- cyclohexane cyclohexanedimethanodibasic effectively acts as difunctional effect, i.e. as the heat stabilizer of PVC and plasticizer, while the thermal stability for enhancing PVC, good plasticity is also made it have.
Description
Technical field
The present invention relates to the production technical fields of heat stabilizer, and in particular to a kind of sheet calcium-zinc composite stabilizing agent and its life
Production. art process.
Background technique
Polyvinyl chloride is one of five big synthetic resin general in the world, and dosage is maximum, extensive with superior performance
For every field such as construction industry, agricultural, daily necessities.Processing heat stability is poor when due to PVC high temperature, must in its processing and forming
Heat stabilizer must be added to maintain its performance.
In a broad aspect, can increase solution, colloid, solid, mixture stability chemicals be all stabilizer.Stabilizer
The effects of reaction can be slowed down, chemical balance is kept, reduce surface tension, prevent light, thermal decomposition or oxygenolysis.The change of broad sense
It is very extensive to learn stabilizer source, mainly according to the purpose of design of fonnulator, can flexibly using any chemicals with
Achieve the purpose that PVC product with stable quality.Industrial common heat stabilizer mainly includes lead salt, metallic soap, organotin, organic
Antimony, organic RE, pure organic compound etc..It is estimated that there is 70,000 t/a of heat stabilizer production capacity in China at present, consume within 2000
Amount is about 80,000 t/a.Mainly there are lead salts and organic tin using most heat stabilizers in traditional PVC production, but there is poison
Property it is big and expensive the problems such as.Novel environment friendly calcium-zinc composite stabilizing agent is environmentally friendly, nontoxic and efficient due to having many advantages, such as,
As kind most with prospects.Currently, import calcium zinc stabilizer is expensive, domestic calcium zinc stabilizer is chiefly used in a certain
In specific PVC industry, and there are the cyclohexadione compounds for easily causing PVC product discoloration in ingredient mostly, has potential
Risk.
In field of plastics processing, the additive amount of auxiliary agent can influence the performance of plastics less as far as possible to avoid addition auxiliary agent；It opens
Send out auxiliary agent high performance and be the direction that this field is studied always；Metallic compound with lewis acid structure is to PVC degradation table
Reveal strong catalytic action, such as ZnCl2, this leads to poor long-term thermal stability.Therefore, it is led in heat stabilizer technology
On the one hand domain widens the type of heat stabilizer, improves the thermal stability of heat stabilizer, on the other hand develop a kind of environmentally friendly and high
The heat stabilizer of effect has great importance for the processing of plastics.
Summary of the invention
In order to solve technological deficiency existing for the PVC lead heat stabilizer and organo-tin het stabilizer that the existing country uses and
Solve the problems, such as PVC heat resistance be poor in process, delay " the zinc burning " of PVC, it is excellent that the present invention provides a kind of performance
Sheet calcium-zinc composite stabilizing agent different, with heat stabilizer and the difunctional effect of plasticizer and its technological process of production.
In order to achieve the above object, the present invention provides the following technical solutions, a kind of sheet calcium-zinc composite stabilizing agent, above-mentioned
Raw material of the PVC with calcium-zinc composite stabilizing agent comprising following parts by weight of component: 10-30 parts of calcium stearate, cis- -1,2- hexamethylene two
Two 10-30 parts of mannitol ester group zinc metal alkoxide of formic acid, 10-15 parts of auxiliary stabilizer, 5-10 parts of zeolite, 10-20 parts of lubricant,
1-5 parts of antioxidant.
Above-mentioned auxiliary stabilizer includes epoxidised soybean oil and pentaerythrite, and the weight of epoxidised soybean oil and pentaerythrite
Amount portion rate is 1:3.
Above-mentioned zeolite is ultra-fine 4A zeolite.
Above-mentioned lubricant is one or both of polyethylene wax, pentaerythritol stearate.
Above-mentioned antioxidant includes one or both of antioxidant 1010, antioxidant 1076.
A kind of technological process of production of sheet calcium-zinc composite stabilizing agent, includes the following steps:
(1) preparation of calcium stearate: taking stearic acid to be added in reaction kettle, and temperature is maintained at 100 DEG C, is added while stirring
Temperature after the completion of feeding intake, is risen to 130 DEG C, hydrogen peroxide and calper calcium peroxide weight ratio is added as the mixed catalytic of 4:1 by calcium oxide
Agent is stirred to react 40 minutes, is then added sodium hydroxide, and isothermal reaction 15 minutes；Open vacuum pump, adjust vacuum degree to-
0.08MPa is dehydrated, and stablizes reaction 60 minutes under the conditions of constant temperature and pressure, reaction terminating is to get calcium stearate；
(2) preparation of cis- two mannitol ester group zinc metal alkoxide of -1,2- cyclohexane cyclohexanedimethanodibasic: 1. by cis- -1,2- ring
Hexane dicarboxylic acid acid anhydride, d- mannitol, which are introduced into high speed disintegrator, to be crushed after five minutes, and catalyst p-methyl benzenesulfonic acid is introduced,
Continue to crush 15-30 minutes；Then this crushed mixture and hexamethylene are added in the container equipped with mechanical agitator, In
After stirring 3-5 hours under the conditions of 160 DEG C, remaining hexamethylene is removed by distillation, obtains cis- -1,2- cyclohexane cyclohexanedimethanodibasic two
2. obtained cis- two Nitranitol of -1,2- cyclohexane cyclohexanedimethanodibasic and certain mole of zinc acetate are added to and are equipped with by Nitranitol
In the open blender of dehydrated alcohol, mixed slowly under the conditions of 140 DEG C 4 hours；After ethyl alcohol evaporating completely, that is, obtain suitable
Two mannitol ester group zinc metal alkoxide of formula -1,2- cyclohexane cyclohexanedimethanodibasic；
(3) preparation of sheet calcium-zinc composite stabilizing agent: by a certain proportion of calcium stearate, cis- -1,2- hexamethylene diformazan
Sour two mannitol ester group zinc metal alkoxides, auxiliary stabilizer, zeolite, lubricant, antioxidant are added in reaction vessel and uniformly stir
It mixes, keeping reaction temperature is 60 DEG C, and the mixture stirred evenly is imported in double edging press and cools down and is squeezed into solid-state sheet
Then sheet finished product is packaged by finished product.
The additional amount of calcium oxide is the 10% of stearic acid quality in above-mentioned steps (1)；Catalyst adds in above-mentioned steps (1)
Enter 5% that amount is stearic acid quality；The additional amount of sodium hydroxide is the 0.2% of stearic acid quality in above-mentioned steps (1).
Cis- -1,2- cyclohexane cyclohexanedimethanodibasic acid anhydride in above-mentioned steps (2): d- mannitol weight ratio is 1:2.5.
Compared with prior art, the beneficial effect of a kind of sheet calcium-zinc composite stabilizing agent of the present invention and its technological process of production
It is:
(1) sheet calcium-zinc composite stabilizing agent of the invention, with calcium stearate and cis- -1,2- cyclohexane cyclohexanedimethanodibasic, two sweet dew
Alcohol ester group zinc metal alkoxide is main stabilizer, and cis- -1,2- cyclohexane cyclohexanedimethanodibasic, two mannitol ester group zinc metal alkoxide, it can
Effectively effectively to absorb HCl and replace the unstable chlorine atom on PVC chain；In addition, hydroxyl abundant can be with life on its molecule
At ZnCl2Chelate is formed, to prevent " zinc burning ".
(2) sheet calcium-zinc composite stabilizing agent of the invention, cis- -1,2- cyclohexane cyclohexanedimethanodibasic, two mannitol ester group zinc metal
The cyclohexanedicarboxyester ester that alkoxide derives is nontoxic and environmentally friendly plasticizer, is had and the comparable property of toxic phthalic acid ester
Energy；Mannitol is a kind of widely used food additives and drug.Therefore cis- two Nitranitol of -1,2- cyclohexane cyclohexanedimethanodibasic
Base zinc metal alkoxide is a kind of very promising thermostabilization and is plasticized difunctional PVC heat stabilizer.
(3) sheet calcium-zinc composite stabilizing agent of the invention, without heavy metals objects such as lead class, tin classes in this stabiliser system
Matter meets nontoxic, environmentally friendly theory.
(4) technological process of production of sheet calcium-zinc composite stabilizing agent of the invention is simple, strong operability.
Detailed description of the invention
Fig. 1 is a kind of production technological process of sheet calcium-zinc composite stabilizing agent of the present invention；
Fig. 2 is the preparation flow figure of the cis- two mannitol ester group zinc metal alkoxide of -1,2- cyclohexane cyclohexanedimethanodibasic of the present invention；
Fig. 3 is the congo red method test result figure of various embodiments of the present invention；
Fig. 4 is the oven heat method test result figure of various embodiments of the present invention；
Fig. 5 is the torque rheology test result figure of the embodiment of the present invention 8 and PVC master batch.
Specific embodiment
Below in conjunction with the embodiment of the present invention, clear, complete description is carried out to technical solution of the present invention, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Every other embodiment obtained by those of ordinary skill in the art without making creative efforts, belongs to this hair
The range of bright protection.
Embodiment 1:
The preparation of calcium stearate: stearic acid (6.5g) is taken to be added in reaction kettle, temperature is maintained at 100 DEG C, while stirring
It is added calcium oxide (0.65g), after the completion of feeding intake, temperature is risen to 130 DEG C, it is 4 that hydrogen peroxide and calper calcium peroxide weight ratio, which is added:
1 mixed catalyst (0.32g) is stirred to react 40 minutes, sodium hydroxide (0.013g) then is added, and isothermal reaction 15 minutes；
Vacuum pump is opened, vacuum degree is adjusted to -0.08MPa, is dehydrated, stable reaction 60 minutes under the conditions of constant temperature and pressure, reaction terminating, i.e.,
It obtains calcium stearate (5.8g).
The preparation of cis- two mannitol ester group zinc metal alkoxide of -1,2- cyclohexane cyclohexanedimethanodibasic: 1. by cis- -1,2- hexamethylene
Dicarboxylic acid anhydride (1.9g), d- mannitol (4.75g) are introduced into high speed disintegrator and crush after five minutes, by catalyst to methylbenzene
Sulfonic acid (0.03g) introduces, and continues to crush 30 minutes；Then this crushed mixture and hexamethylene are added to equipped with mechanical agitator
Container in, after stirring 4 hours under the conditions of 160 DEG C, remaining hexamethylene is removed by distillation, obtains cis- -1,2- hexamethylene
Two Nitranitol of alkane dioctyl phthalate (6.0g) is 2. by obtained cis- two Nitranitol of -1,2- cyclohexane cyclohexanedimethanodibasic (6.0g) and acetic acid
Zinc (1.1g) is added in the open blender equipped with dehydrated alcohol, is mixed slowly under the conditions of 140 DEG C 4 hours；When ethyl alcohol is complete
After pervaporation, that is, obtain cis- -1,2- cyclohexane cyclohexanedimethanodibasic, two mannitol ester group zinc metal alkoxide A (6.01g) (cis- -1,2-
The molar ratio of two Nitranitol of cyclohexane cyclohexanedimethanodibasic and zinc acetate is 2:1).
The preparation of sheet calcium-zinc composite stabilizing agent: by 30 parts of calcium stearate, 15 parts of auxiliary stabilizer, 5 parts of zeolite, lubricant
10 parts, 3 parts of antioxidant are added to uniform stirring in reaction vessel, and wherein lubricant is the polyethylene wax and season that weight ratio is 1:1
The compounding of penta tetrol stearate, antioxidant are antioxidant 1010；Keeping reaction temperature is 60 DEG C, the mixture that will be stirred evenly
It imports in double edging press and cools down and be squeezed into solid-state sheet finished product, be then packaged sheet finished product.
Embodiment 2:
The preparation of calcium stearate: stearic acid (6.5g) is taken to be added in reaction kettle, temperature is maintained at 100 DEG C, while stirring
It is added calcium oxide (0.65g), after the completion of feeding intake, temperature is risen to 130 DEG C, it is 4 that hydrogen peroxide and calper calcium peroxide weight ratio, which is added:
1 mixed catalyst (0.32g) is stirred to react 40 minutes, sodium hydroxide (0.013g) then is added, and isothermal reaction 15 minutes；
Vacuum pump is opened, vacuum degree is adjusted to -0.08MPa, is dehydrated, stable reaction 60 minutes under the conditions of constant temperature and pressure, reaction terminating, i.e.,
It obtains calcium stearate (5.8g).
The preparation of cis- two mannitol ester group zinc metal alkoxide of -1,2- cyclohexane cyclohexanedimethanodibasic: 1. by cis- -1,2- hexamethylene
Dicarboxylic acid anhydride (1.9g), d- mannitol (4.75g) are introduced into high speed disintegrator and crush after five minutes, by catalyst to methylbenzene
Sulfonic acid (0.03g) introduces, and continues to crush 30 minutes；Then this crushed mixture and hexamethylene are added to equipped with mechanical agitator
Container in, after stirring 4 hours under the conditions of 160 DEG C, remaining hexamethylene is removed by distillation, obtains cis- -1,2- hexamethylene
Two Nitranitol of alkane dioctyl phthalate (6.0g) is 2. by obtained cis- two Nitranitol of -1,2- cyclohexane cyclohexanedimethanodibasic (6.0g) and acetic acid
Zinc (1.1g) is added in the open blender equipped with dehydrated alcohol, is mixed slowly under the conditions of 140 DEG C 4 hours；When ethyl alcohol is complete
After pervaporation, that is, obtain cis- -1,2- cyclohexane cyclohexanedimethanodibasic, two mannitol ester group zinc metal alkoxide A (6.01g) (cis- -1,2-
The molar ratio of two Nitranitol of cyclohexane cyclohexanedimethanodibasic and zinc acetate is 2:1).
The preparation of sheet calcium-zinc composite stabilizing agent: by 20 parts of calcium stearate, cis- two mannitol of -1,2- cyclohexane cyclohexanedimethanodibasic
A10 parts of ester group zinc metal alkoxide, 15 parts of auxiliary stabilizer, 5 parts of zeolite, 10 parts of lubricant, 3 parts of antioxidant be added to reaction vessel
Middle uniform stirring, wherein lubricant is the compounding of polyethylene wax and pentaerythritol stearate that weight ratio is 1:1, and antioxidant is
Antioxidant 1010；Keeping reaction temperature is 60 DEG C, and the mixture stirred evenly is imported in double edging press and cools down and is squeezed into
Sheet finished product, is then packaged by solid-state sheet finished product.
Embodiment 3:
The preparation of calcium stearate: stearic acid (6.5g) is taken to be added in reaction kettle, temperature is maintained at 100 DEG C, while stirring
It is added calcium oxide (0.65g), after the completion of feeding intake, temperature is risen to 130 DEG C, it is 4 that hydrogen peroxide and calper calcium peroxide weight ratio, which is added:
1 mixed catalyst (0.32g) is stirred to react 40 minutes, sodium hydroxide (0.013g) then is added, and isothermal reaction 15 minutes；
Vacuum pump is opened, vacuum degree is adjusted to -0.08MPa, is dehydrated, stable reaction 60 minutes under the conditions of constant temperature and pressure, reaction terminating, i.e.,
It obtains calcium stearate (5.8g).
The preparation of cis- two mannitol ester group zinc metal alkoxide of -1,2- cyclohexane cyclohexanedimethanodibasic: 1. by cis- -1,2- hexamethylene
Dicarboxylic acid anhydride (1.9g), d- mannitol (4.75g) are introduced into high speed disintegrator and crush after five minutes, by catalyst to methylbenzene
Sulfonic acid (0.03g) introduces, and continues to crush 30 minutes；Then this crushed mixture and hexamethylene are added to equipped with mechanical agitator
Container in, after stirring 4 hours under the conditions of 160 DEG C, remaining hexamethylene is removed by distillation, obtains cis- -1,2- hexamethylene
Two Nitranitol of alkane dioctyl phthalate (6.0g) is 2. by obtained cis- two Nitranitol of -1,2- cyclohexane cyclohexanedimethanodibasic (6.0g) and acetic acid
Zinc (1.1g) is added in the open blender equipped with dehydrated alcohol, is mixed slowly under the conditions of 140 DEG C 4 hours；When ethyl alcohol is complete
After pervaporation, that is, obtain cis- -1,2- cyclohexane cyclohexanedimethanodibasic, two mannitol ester group zinc metal alkoxide A (6.01g) (cis- -1,2-
The molar ratio of two Nitranitol of cyclohexane cyclohexanedimethanodibasic and zinc acetate is 2:1).
The preparation of sheet calcium-zinc composite stabilizing agent: by 10 parts of calcium stearate, cis- two mannitol of -1,2- cyclohexane cyclohexanedimethanodibasic
A20 parts of ester group zinc metal alkoxide, 15 parts of auxiliary stabilizer, 5 parts of zeolite, 10 parts of lubricant, 3 parts of antioxidant be added to reaction vessel
Middle uniform stirring, wherein lubricant is the compounding of polyethylene wax and pentaerythritol stearate that weight ratio is 1:1, and antioxidant is
Antioxidant 1010；Keeping reaction temperature is 60 DEG C, and the mixture stirred evenly is imported in double edging press and cools down and is squeezed into
Sheet finished product, is then packaged by solid-state sheet finished product.
Embodiment 4:
The preparation of calcium stearate: stearic acid (6.5g) is taken to be added in reaction kettle, temperature is maintained at 100 DEG C, while stirring
It is added calcium oxide (0.65g), after the completion of feeding intake, temperature is risen to 130 DEG C, it is 4 that hydrogen peroxide and calper calcium peroxide weight ratio, which is added:
1 mixed catalyst (0.32g) is stirred to react 40 minutes, sodium hydroxide (0.013g) then is added, and isothermal reaction 15 minutes；
Vacuum pump is opened, vacuum degree is adjusted to -0.08MPa, is dehydrated, stable reaction 60 minutes under the conditions of constant temperature and pressure, reaction terminating, i.e.,
It obtains calcium stearate (5.8g).
The preparation of cis- two mannitol ester group zinc metal alkoxide of -1,2- cyclohexane cyclohexanedimethanodibasic: 1. by cis- -1,2- hexamethylene
Dicarboxylic acid anhydride (1.9g), d- mannitol (4.75g) are introduced into high speed disintegrator and crush after five minutes, by catalyst to methylbenzene
Sulfonic acid (0.03g) introduces, and continues to crush 30 minutes；Then this crushed mixture and hexamethylene are added to equipped with mechanical agitator
Container in, after stirring 4 hours under the conditions of 160 DEG C, remaining hexamethylene is removed by distillation, obtains cis- -1,2- hexamethylene
Two Nitranitol of alkane dioctyl phthalate (6.0g) is 2. by obtained cis- two Nitranitol of -1,2- cyclohexane cyclohexanedimethanodibasic (6.0g) and acetic acid
Zinc (1.1g) is added in the open blender equipped with dehydrated alcohol, is mixed slowly under the conditions of 140 DEG C 4 hours；When ethyl alcohol is complete
After pervaporation, that is, obtain cis- -1,2- cyclohexane cyclohexanedimethanodibasic, two mannitol ester group zinc metal alkoxide A (6.01g) (cis- -1,2-
The molar ratio of two Nitranitol of cyclohexane cyclohexanedimethanodibasic and zinc acetate is 2:1).
The preparation of sheet calcium-zinc composite stabilizing agent: by cis- two mannitol ester group zinc metal alcohol of -1,2- cyclohexane cyclohexanedimethanodibasic
A30 parts of salt, 15 parts of auxiliary stabilizer, 5 parts of zeolite, 10 parts of lubricant, 3 parts of antioxidant be added to uniform stirring in reaction vessel,
Wherein lubricant is the compounding of polyethylene wax and pentaerythritol stearate that weight ratio is 1:1, and antioxidant is antioxidant 1010；
Keeping reaction temperature is 60 DEG C, the mixture stirred evenly is imported in double edging press cool down and be squeezed into solid-state sheet at
Then sheet finished product is packaged by product.
Embodiment 5:
The preparation of calcium stearate: stearic acid (6.5g) is taken to be added in reaction kettle, temperature is maintained at 100 DEG C, while stirring
It is added calcium oxide (0.65g), after the completion of feeding intake, temperature is risen to 130 DEG C, it is 4 that hydrogen peroxide and calper calcium peroxide weight ratio, which is added:
1 mixed catalyst (0.32g) is stirred to react 40 minutes, sodium hydroxide (0.013g) then is added, and isothermal reaction 15 minutes；
Vacuum pump is opened, vacuum degree is adjusted to -0.08MPa, is dehydrated, stable reaction 60 minutes under the conditions of constant temperature and pressure, reaction terminating, i.e.,
It obtains calcium stearate (5.8g).
The preparation of cis- two mannitol ester group zinc metal alkoxide of -1,2- cyclohexane cyclohexanedimethanodibasic: 1. by cis- -1,2- hexamethylene
Dicarboxylic acid anhydride (1.9g), d- mannitol (4.75g) are introduced into high speed disintegrator and crush after five minutes, by catalyst to methylbenzene
Sulfonic acid (0.03g) introduces, and continues to crush 30 minutes；Then this crushed mixture and hexamethylene are added to equipped with mechanical agitator
Container in, after stirring 4 hours under the conditions of 160 DEG C, remaining hexamethylene is removed by distillation, obtains cis- -1,2- hexamethylene
Two Nitranitol of alkane dioctyl phthalate (6.0g) is 2. by obtained cis- two Nitranitol of -1,2- cyclohexane cyclohexanedimethanodibasic (6.0g) and acetic acid
Zinc (2.2g) is added in the open blender equipped with dehydrated alcohol, is mixed slowly under the conditions of 140 DEG C 4 hours；When ethyl alcohol is complete
After pervaporation, that is, obtain cis- -1,2- cyclohexane cyclohexanedimethanodibasic, two mannitol ester group zinc metal alkoxide B (6.37g) (cis- -1,2-
The molar ratio of two Nitranitol of cyclohexane cyclohexanedimethanodibasic and zinc acetate is 1:1).
The preparation of sheet calcium-zinc composite stabilizing agent: by 10 parts of calcium stearate, cis- two mannitol of -1,2- cyclohexane cyclohexanedimethanodibasic
A20 parts of ester group zinc metal alkoxide, 15 parts of auxiliary stabilizer, 5 parts of zeolite, 10 parts of lubricant, 3 parts of antioxidant be added to reaction vessel
Middle uniform stirring, wherein lubricant is the compounding of polyethylene wax and pentaerythritol stearate that weight ratio is 1:1, and antioxidant is
Antioxidant 1010；Keeping reaction temperature is 60 DEG C, and the mixture stirred evenly is imported in double edging press and cools down and is squeezed into
Sheet finished product, is then packaged by solid-state sheet finished product.
Embodiment 6:
The preparation of calcium stearate: stearic acid (6.5g) is taken to be added in reaction kettle, temperature is maintained at 100 DEG C, while stirring
It is added calcium oxide (0.65g), after the completion of feeding intake, temperature is risen to 130 DEG C, it is 4 that hydrogen peroxide and calper calcium peroxide weight ratio, which is added:
1 mixed catalyst (0.32g) is stirred to react 40 minutes, sodium hydroxide (0.013g) then is added, and isothermal reaction 15 minutes；
Vacuum pump is opened, vacuum degree is adjusted to -0.08MPa, is dehydrated, stable reaction 60 minutes under the conditions of constant temperature and pressure, reaction terminating, i.e.,
It obtains calcium stearate (5.8g).
The preparation of cis- two mannitol ester group zinc metal alkoxide of -1,2- cyclohexane cyclohexanedimethanodibasic: 1. by cis- -1,2- hexamethylene
Dicarboxylic acid anhydride (1.9g), d- mannitol (4.75g) are introduced into high speed disintegrator and crush after five minutes, by catalyst to methylbenzene
Sulfonic acid (0.03g) introduces, and continues to crush 30 minutes；Then this crushed mixture and hexamethylene are added to equipped with mechanical agitator
Container in, after stirring 4 hours under the conditions of 160 DEG C, remaining hexamethylene is removed by distillation, obtains cis- -1,2- hexamethylene
Two Nitranitol of alkane dioctyl phthalate (6.0g) is 2. by obtained cis- two Nitranitol of -1,2- cyclohexane cyclohexanedimethanodibasic (6.0g) and acetic acid
Zinc (4.4g) is added in the open blender equipped with dehydrated alcohol, is mixed slowly under the conditions of 140 DEG C 4 hours；When ethyl alcohol is complete
After pervaporation, that is, obtain cis- -1,2- cyclohexane cyclohexanedimethanodibasic, two mannitol ester group zinc metal alkoxide C (7.02g) (cis- -1,2-
The molar ratio of two Nitranitol of cyclohexane cyclohexanedimethanodibasic and zinc acetate is 1:2).
The preparation of sheet calcium-zinc composite stabilizing agent: by 10 parts of calcium stearate, cis- two mannitol of -1,2- cyclohexane cyclohexanedimethanodibasic
A20 parts of ester group zinc metal alkoxide, 15 parts of auxiliary stabilizer, 5 parts of zeolite, 10 parts of lubricant, 3 parts of antioxidant be added to reaction vessel
Middle uniform stirring, wherein lubricant is the compounding of polyethylene wax and pentaerythritol stearate that weight ratio is 1:1, and antioxidant is
Antioxidant 1010；Keeping reaction temperature is 60 DEG C, and the mixture stirred evenly is imported in double edging press and cools down and is squeezed into
Sheet finished product, is then packaged by solid-state sheet finished product.
Embodiment 7:
The preparation of calcium stearate: stearic acid (6.5g) is taken to be added in reaction kettle, temperature is maintained at 100 DEG C, while stirring
It is added calcium oxide (0.65g), after the completion of feeding intake, temperature is risen to 130 DEG C, it is 4 that hydrogen peroxide and calper calcium peroxide weight ratio, which is added:
1 mixed catalyst (0.32g) is stirred to react 40 minutes, sodium hydroxide (0.013g) then is added, and isothermal reaction 15 minutes；
Vacuum pump is opened, vacuum degree is adjusted to -0.08MPa, is dehydrated, stable reaction 60 minutes under the conditions of constant temperature and pressure, reaction terminating, i.e.,
It obtains calcium stearate (5.8g).
The preparation of cis- two mannitol ester group zinc metal alkoxide of -1,2- cyclohexane cyclohexanedimethanodibasic: 1. by cis- -1,2- hexamethylene
Dicarboxylic acid anhydride (1.9g), d- mannitol (4.75g) are introduced into high speed disintegrator and crush after five minutes, by catalyst to methylbenzene
Sulfonic acid (0.03g) introduces, and continues to crush 30 minutes；Then this crushed mixture and hexamethylene are added to equipped with mechanical agitator
Container in, after stirring 4 hours under the conditions of 160 DEG C, remaining hexamethylene is removed by distillation, obtains cis- -1,2- hexamethylene
Two Nitranitol of alkane dioctyl phthalate (6.0g) is 2. by obtained cis- two Nitranitol of -1,2- cyclohexane cyclohexanedimethanodibasic (6.0g) and acetic acid
Zinc (2.2g) is added in the open blender equipped with dehydrated alcohol, is mixed slowly under the conditions of 140 DEG C 4 hours；When ethyl alcohol is complete
After pervaporation, that is, obtain cis- -1,2- cyclohexane cyclohexanedimethanodibasic, two mannitol ester group zinc metal alkoxide B (6.37g) (cis- -1,2-
The molar ratio of two Nitranitol of cyclohexane cyclohexanedimethanodibasic and zinc acetate is 1:1).
The preparation of sheet calcium-zinc composite stabilizing agent: by 10 parts of calcium stearate, cis- two mannitol of -1,2- cyclohexane cyclohexanedimethanodibasic
A20 parts of ester group zinc metal alkoxide, 10 parts of auxiliary stabilizer, 5 parts of zeolite, 10 parts of lubricant, 3 parts of antioxidant be added to reaction vessel
Middle uniform stirring, wherein lubricant is the compounding of polyethylene wax and pentaerythritol stearate that weight ratio is 1:1, and antioxidant is
Antioxidant 1010；Keeping reaction temperature is 60 DEG C, and the mixture stirred evenly is imported in double edging press and cools down and is squeezed into
Sheet finished product, is then packaged by solid-state sheet finished product.
Embodiment 8:
The preparation of calcium stearate: stearic acid (6.5g) is taken to be added in reaction kettle, temperature is maintained at 100 DEG C, while stirring
It is added calcium oxide (0.65g), after the completion of feeding intake, temperature is risen to 130 DEG C, it is 4 that hydrogen peroxide and calper calcium peroxide weight ratio, which is added:
1 mixed catalyst (0.32g) is stirred to react 40 minutes, sodium hydroxide (0.013g) then is added, and isothermal reaction 15 minutes；
Vacuum pump is opened, vacuum degree is adjusted to -0.08MPa, is dehydrated, stable reaction 60 minutes under the conditions of constant temperature and pressure, reaction terminating, i.e.,
It obtains calcium stearate (5.8g).
The preparation of cis- two mannitol ester group zinc metal alkoxide of -1,2- cyclohexane cyclohexanedimethanodibasic: 1. by cis- -1,2- hexamethylene
Dicarboxylic acid anhydride (1.9g), d- mannitol (4.75g) are introduced into high speed disintegrator and crush after five minutes, by catalyst to methylbenzene
Sulfonic acid (0.03g) introduces, and continues to crush 30 minutes；Then this crushed mixture and hexamethylene are added to equipped with mechanical agitator
Container in, after stirring 4 hours under the conditions of 160 DEG C, remaining hexamethylene is removed by distillation, obtains cis- -1,2- hexamethylene
Two Nitranitol of alkane dioctyl phthalate (6.0g) is 2. by obtained cis- two Nitranitol of -1,2- cyclohexane cyclohexanedimethanodibasic (6.0g) and acetic acid
Zinc (2.2g) is added in the open blender equipped with dehydrated alcohol, is mixed slowly under the conditions of 140 DEG C 4 hours；When ethyl alcohol is complete
After pervaporation, that is, obtain cis- -1,2- cyclohexane cyclohexanedimethanodibasic, two mannitol ester group zinc metal alkoxide B (6.37g) (cis- -1,2-
The molar ratio of two Nitranitol of cyclohexane cyclohexanedimethanodibasic and zinc acetate is 1:1).
The preparation of sheet calcium-zinc composite stabilizing agent: by 10 parts of calcium stearate, cis- two mannitol of -1,2- cyclohexane cyclohexanedimethanodibasic
A20 parts of ester group zinc metal alkoxide, 15 parts of auxiliary stabilizer, 10 parts of zeolite, 10 parts of lubricant, 3 parts of antioxidant be added to reaction hold
Uniform stirring in device, wherein lubricant is the compounding of polyethylene wax and pentaerythritol stearate that weight ratio is 1:1, antioxidant
For antioxidant 1010；Keeping reaction temperature is 60 DEG C, and the mixture stirred evenly is imported in double edging press and cools down and squeezes
At solid-state sheet finished product, then sheet finished product is packaged.
Embodiment 9:
The preparation of calcium stearate: stearic acid (6.5g) is taken to be added in reaction kettle, temperature is maintained at 100 DEG C, while stirring
It is added calcium oxide (0.65g), after the completion of feeding intake, temperature is risen to 130 DEG C, it is 4 that hydrogen peroxide and calper calcium peroxide weight ratio, which is added:
1 mixed catalyst (0.32g) is stirred to react 40 minutes, sodium hydroxide (0.013g) then is added, and isothermal reaction 15 minutes；
Vacuum pump is opened, vacuum degree is adjusted to -0.08MPa, is dehydrated, stable reaction 60 minutes under the conditions of constant temperature and pressure, reaction terminating, i.e.,
It obtains calcium stearate (5.8g).
The preparation of cis- two mannitol ester group zinc metal alkoxide of -1,2- cyclohexane cyclohexanedimethanodibasic: 1. by cis- -1,2- hexamethylene
Dicarboxylic acid anhydride (1.9g), d- mannitol (4.75g) are introduced into high speed disintegrator and crush after five minutes, by catalyst to methylbenzene
Sulfonic acid (0.03g) introduces, and continues to crush 30 minutes；Then this crushed mixture and hexamethylene are added to equipped with mechanical agitator
Container in, after stirring 4 hours under the conditions of 160 DEG C, remaining hexamethylene is removed by distillation, obtains cis- -1,2- hexamethylene
Two Nitranitol of alkane dioctyl phthalate (6.0g) is 2. by obtained cis- two Nitranitol of -1,2- cyclohexane cyclohexanedimethanodibasic (6.0g) and acetic acid
Zinc (2.2g) is added in the open blender equipped with dehydrated alcohol, is mixed slowly under the conditions of 140 DEG C 4 hours；When ethyl alcohol is complete
After pervaporation, that is, obtain cis- -1,2- cyclohexane cyclohexanedimethanodibasic, two mannitol ester group zinc metal alkoxide B (6.37g) (cis- -1,2-
The molar ratio of two Nitranitol of cyclohexane cyclohexanedimethanodibasic and zinc acetate is 1:1).
The preparation of sheet calcium-zinc composite stabilizing agent: by 10 parts of calcium stearate, cis- two mannitol of -1,2- cyclohexane cyclohexanedimethanodibasic
A20 parts of ester group zinc metal alkoxide, 15 parts of auxiliary stabilizer, 10 parts of zeolite, 20 parts of lubricant, 5 parts of antioxidant be added to reaction hold
Uniform stirring in device, wherein lubricant is the compounding of polyethylene wax and pentaerythritol stearate that weight ratio is 1:1, antioxidant
For antioxidant 1010；Keeping reaction temperature is 60 DEG C, and the mixture stirred evenly is imported in double edging press and cools down and squeezes
At solid-state sheet finished product, then sheet finished product is packaged.
Embodiment 10:
The preparation of calcium stearate: stearic acid (6.5g) is taken to be added in reaction kettle, temperature is maintained at 100 DEG C, while stirring
It is added calcium oxide (0.65g), after the completion of feeding intake, temperature is risen to 130 DEG C, it is 4 that hydrogen peroxide and calper calcium peroxide weight ratio, which is added:
1 mixed catalyst (0.32g) is stirred to react 40 minutes, sodium hydroxide (0.013g) then is added, and isothermal reaction 15 minutes；
Vacuum pump is opened, vacuum degree is adjusted to -0.08MPa, is dehydrated, stable reaction 60 minutes under the conditions of constant temperature and pressure, reaction terminating, i.e.,
It obtains calcium stearate (5.8g).
The preparation of cis- two mannitol ester group zinc metal alkoxide of -1,2- cyclohexane cyclohexanedimethanodibasic: 1. by cis- -1,2- hexamethylene
Dicarboxylic acid anhydride (1.9g), d- mannitol (4.75g) are introduced into high speed disintegrator and crush after five minutes, by catalyst to methylbenzene
Sulfonic acid (0.03g) introduces, and continues to crush 30 minutes；Then this crushed mixture and hexamethylene are added to equipped with mechanical agitator
Container in, after stirring 4 hours under the conditions of 160 DEG C, remaining hexamethylene is removed by distillation, obtains cis- -1,2- hexamethylene
Two Nitranitol of alkane dioctyl phthalate (6.0g) is 2. by obtained cis- two Nitranitol of -1,2- cyclohexane cyclohexanedimethanodibasic (6.0g) and acetic acid
Zinc (2.2g) is added in the open blender equipped with dehydrated alcohol, is mixed slowly under the conditions of 140 DEG C 4 hours；When ethyl alcohol is complete
After pervaporation, that is, obtain cis- -1,2- cyclohexane cyclohexanedimethanodibasic, two mannitol ester group zinc metal alkoxide B (6.37g) (cis- -1,2-
The molar ratio of two Nitranitol of cyclohexane cyclohexanedimethanodibasic and zinc acetate is 1:1).
The preparation of sheet calcium-zinc composite stabilizing agent: by 10 parts of calcium stearate, cis- two mannitol of -1,2- cyclohexane cyclohexanedimethanodibasic
A20 parts of ester group zinc metal alkoxide, 15 parts of auxiliary stabilizer, 10 parts of zeolite, 10 parts of lubricant, 3 parts of antioxidant be added to reaction hold
Uniform stirring in device, wherein lubricant is polyethylene wax, and antioxidant is antioxidant 1076；Keeping reaction temperature is 60 DEG C, will be stirred
It mixes in the uniform double edging press of mixture importing and cools down and be squeezed into solid-state sheet finished product, be then packaged sheet finished product.
Embodiment 11:
The preparation of calcium stearate: stearic acid (6.5g) is taken to be added in reaction kettle, temperature is maintained at 100 DEG C, while stirring
It is added calcium oxide (0.65g), after the completion of feeding intake, temperature is risen to 130 DEG C, it is 4 that hydrogen peroxide and calper calcium peroxide weight ratio, which is added:
1 mixed catalyst (0.32g) is stirred to react 40 minutes, sodium hydroxide (0.013g) then is added, and isothermal reaction 15 minutes；
Vacuum pump is opened, vacuum degree is adjusted to -0.08MPa, is dehydrated, stable reaction 60 minutes under the conditions of constant temperature and pressure, reaction terminating, i.e.,
It obtains calcium stearate (5.8g).
The preparation of cis- two mannitol ester group zinc metal alkoxide of -1,2- cyclohexane cyclohexanedimethanodibasic: 1. by cis- -1,2- hexamethylene
Dicarboxylic acid anhydride (1.9g), d- mannitol (4.75g) are introduced into high speed disintegrator and crush after five minutes, by catalyst to methylbenzene
Sulfonic acid (0.03g) introduces, and continues to crush 30 minutes；Then this crushed mixture and hexamethylene are added to equipped with mechanical agitator
Container in, after stirring 4 hours under the conditions of 160 DEG C, remaining hexamethylene is removed by distillation, obtains cis- -1,2- hexamethylene
Two Nitranitol of alkane dioctyl phthalate (6.0g) is 2. by obtained cis- two Nitranitol of -1,2- cyclohexane cyclohexanedimethanodibasic (6.0g) and acetic acid
Zinc (2.2g) is added in the open blender equipped with dehydrated alcohol, is mixed slowly under the conditions of 140 DEG C 4 hours；When ethyl alcohol is complete
After pervaporation, that is, obtain cis- -1,2- cyclohexane cyclohexanedimethanodibasic, two mannitol ester group zinc metal alkoxide B (6.37g) (cis- -1,2-
The molar ratio of two Nitranitol of cyclohexane cyclohexanedimethanodibasic and zinc acetate is 1:1).
The preparation of sheet calcium-zinc composite stabilizing agent: by 10 parts of calcium stearate, cis- two mannitol of -1,2- cyclohexane cyclohexanedimethanodibasic
A20 parts of ester group zinc metal alkoxide, 15 parts of auxiliary stabilizer, 10 parts of zeolite, 10 parts of lubricant, 3 parts of antioxidant be added to reaction hold
Uniform stirring in device, wherein lubricant is pentaerythritol stearate, and antioxidant is the antioxidant 1010 that weight ratio is 1:1 and resists
The compounding of oxygen agent 1076；Keeping reaction temperature is 60 DEG C, and the mixture stirred evenly is imported in double edging press and cools down and squeezes
It is pressed into solid-state sheet finished product, is then packaged sheet finished product.
Existed using sheet calcium-zinc composite stabilizing agent obtained by the above various embodiments and PVC masterbatch with 1:50 weight fraction ratio
Mixing 5 minutes in super mixer；Then it is kneaded 5 minutes on the double roll mill in 180 DEG C；Finally, PVC sheet is obtained,
In so that sheet thickness is maintained at 1.0 ± 0.1mm.Wherein the formula of PVC masterbatch is as follows: 100 parts of polyvinyl chloride (PVC), acrylic acid
2 parts of ester (ACR), calcium carbonate (CaCO3) 20 parts, 2 parts of stearic acid (HSt), titanium dioxide (TiO2) 4 parts and phthalic acid two it is pungent
5 parts of ester (DOP).
It (is tested by GB/T2917-2002 congo red method, when record Congored test paper starts to become blue with congo red method
Between, as static heat-stable time) and oven heat method (PVC print is placed on aluminum trays, is put into 180 DEG C of convection ovens
Heated at constant temperature；PVC print is taken out every 6min, color change is photographed to record, until the complete blackening of PVC print) it examines respectively
The stability and plasticity for surveying the PVC product prepared using sheet calcium-zinc composite stabilizing agent made from embodiment 1-11 are surveyed
Examination.As a result as shown in figure 3, figure 4 and figure 5, the PVC product to be measured as made from the sheet calcium-zinc composite stabilizing agent of embodiment 1-4 is rigid
The discovery of arnotto measurement result, static heat stability can be with cis- -1,2- cyclohexane cyclohexanedimethanodibasic, two mannitol ester group zinc metal
The ratio of alkoxide first increases to be declined afterwards；Cis- -1,2- hexamethylene diformazan is found by the measurement result of embodiment 3 and embodiment 5,6
Zn content ratio has significant shadow to its static heat stability and long-term thermal stability in sour two mannitol ester group zinc metal alkoxides
It rings；It is learnt by the measurement result of embodiment 5 and embodiment 7,11, the addition of auxiliary stabilizer obtains the initial whiteness of PVC sample
To improving slightly, but there is no significant impact to the long-time stability of PVC sample.As the rheology testing of Fig. 5 uses 185
50 revs/min at DEG C, the time torque rheology test result that obtains after twenty minutes；Utilize sheet calcium prepared in embodiment 8
Zinc composite stabilizer is for the rheological curve of PVC product and the rheological curve of pure PVC master batch；The result shows that pure PVC master batch needs
Plasticizing could be completed within about 70 seconds, and in the PVC product stable by sheet calcium-zinc composite stabilizing agent prepared in embodiment 8
In, plasticizing is completed in 30 seconds, it was confirmed that the plasticization of sheet calcium-zinc composite stabilizing agent of the invention to PVC.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding a variety of to the progress of these embodiments can change in the case where not departing from principle and spirit of the invention, modify, replace
It changes and modification, the scope of the present invention is defined by the appended.
Claims (8)
1. a kind of sheet calcium-zinc composite stabilizing agent, which is characterized in that PVC calcium-zinc composite stabilizing agent includes following parts by weight
The raw material of component: 10-30 parts of calcium stearate, two mannitol ester group zinc metal alkoxide 10-30 of cis- -1,2- cyclohexane cyclohexanedimethanodibasic
Part, 10-15 parts of auxiliary stabilizer, 5-10 parts of zeolite, 10-20 parts of lubricant, 1-5 parts of antioxidant.
2. a kind of sheet calcium-zinc composite stabilizing agent according to claim 1, it is characterised in that: the auxiliary stabilizer includes
Epoxidised soybean oil and pentaerythrite, and the weight fraction ratio of epoxidised soybean oil and pentaerythrite is 1:3.
3. a kind of sheet calcium-zinc composite stabilizing agent according to claim 1, it is characterised in that: the zeolite is ultra-fine 4A boiling
Stone.
4. a kind of sheet calcium-zinc composite stabilizing agent according to claim 1, it is characterised in that: the lubricant is polyethylene
One or both of wax, pentaerythritol stearate.
5. a kind of sheet calcium-zinc composite stabilizing agent according to claim 1, it is characterised in that: the antioxidant includes antioxygen
One or both of agent 1010, antioxidant 1076.
6. a kind of technological process of production of sheet calcium-zinc composite stabilizing agent according to claim 1-5, feature exist
In including the following steps:
(1) preparation of calcium stearate: taking stearic acid to be added in reaction kettle, and temperature is maintained at 100 DEG C, and oxidation is added while stirring
Temperature after the completion of feeding intake, is risen to 130 DEG C by calcium, hydrogen peroxide is added and mixed catalyst that calper calcium peroxide weight ratio is 4:1,
It is stirred to react 40 minutes, is then added sodium hydroxide, isothermal reaction 15 minutes；Open vacuum pump, adjust vacuum degree to-
0.08MPa is dehydrated, and stablizes reaction 60 minutes under the conditions of constant temperature and pressure, reaction terminating is to get calcium stearate；
(2) preparation of cis- two mannitol ester group zinc metal alkoxide of -1,2- cyclohexane cyclohexanedimethanodibasic: 1. by cis- -1,2- hexamethylene
Dicarboxylic acid anhydride, d- mannitol, which are introduced into high speed disintegrator, to be crushed after five minutes, and catalyst p-methyl benzenesulfonic acid is introduced, and is continued
It crushes 15-30 minutes；Then this crushed mixture and hexamethylene are added in the container equipped with mechanical agitator, at 160 DEG C
Under the conditions of stir 3-5 hours after, remaining hexamethylene is removed by distillation, obtains cis- -1,2- cyclohexane cyclohexanedimethanodibasic, two sweet dew
2. obtained cis- two Nitranitol of -1,2- cyclohexane cyclohexanedimethanodibasic and certain mole of zinc acetate are added to equipped with anhydrous by alcohol ester
In the open blender of ethyl alcohol, mixed slowly under the conditions of 140 DEG C 4 hours；After ethyl alcohol evaporating completely, that is, cis- -1 is obtained,
Two mannitol ester group zinc metal alkoxide of 2- cyclohexane cyclohexanedimethanodibasic；
(3) preparation of sheet calcium-zinc composite stabilizing agent: by a certain proportion of calcium stearate, cis- -1,2- cyclohexane cyclohexanedimethanodibasic two
Mannitol ester group zinc metal alkoxide, auxiliary stabilizer, zeolite, lubricant, antioxidant are added to uniform stirring in reaction vessel, protect
Holding reaction temperature is 60 DEG C, and the mixture stirred evenly is imported in double edging press and cools down and be squeezed into solid-state sheet finished product,
Then sheet finished product is packaged.
7. a kind of technological process of production of sheet calcium-zinc composite stabilizing agent according to claim 6, it is characterised in that: described
The additional amount of calcium oxide is the 10% of stearic acid quality in step (1)；The additional amount of catalyst is stearic acid in the step (1)
The 5% of quality；The additional amount of sodium hydroxide is the 0.2% of stearic acid quality in the step (1).
8. a kind of technological process of production of sheet calcium-zinc composite stabilizing agent according to claim 6, it is characterised in that: described
Cis- -1,2- cyclohexane cyclohexanedimethanodibasic acid anhydride in step (2): d- mannitol weight ratio is 1:2.5.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112940347A (en) * | 2019-12-10 | 2021-06-11 | 黄山佳宝新材料科技有限公司 | Efficient anti-precipitation powder zinc-based PVC heat stabilizer and preparation method thereof |
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|---|---|---|---|---|
| CN102070857A (en) * | 2010-12-22 | 2011-05-25 | 西南大学 | Calcium-zinc compound stabilizer for polyvinyl chloride (PVC) and preparation method of calcium-zinc compound stabilizer |
| CN105949048A (en) * | 2016-05-23 | 2016-09-21 | 惠州市志海新威科技有限公司 | Calcium stearate and preparation process thereof |
| CN108410091A (en) * | 2018-04-09 | 2018-08-17 | 河源市鑫达科技有限公司 | A kind of PVC heat stabilizer based on polyol ester metal complex |
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2019
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| CN102070857A (en) * | 2010-12-22 | 2011-05-25 | 西南大学 | Calcium-zinc compound stabilizer for polyvinyl chloride (PVC) and preparation method of calcium-zinc compound stabilizer |
| CN105949048A (en) * | 2016-05-23 | 2016-09-21 | 惠州市志海新威科技有限公司 | Calcium stearate and preparation process thereof |
| CN108410091A (en) * | 2018-04-09 | 2018-08-17 | 河源市鑫达科技有限公司 | A kind of PVC heat stabilizer based on polyol ester metal complex |
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| CN112940347A (en) * | 2019-12-10 | 2021-06-11 | 黄山佳宝新材料科技有限公司 | Efficient anti-precipitation powder zinc-based PVC heat stabilizer and preparation method thereof |
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