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CN114773748A - Composition containing tributyl aconitate and application thereof - Google Patents

Composition containing tributyl aconitate and application thereof Download PDF

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Publication number
CN114773748A
CN114773748A CN202210413333.1A CN202210413333A CN114773748A CN 114773748 A CN114773748 A CN 114773748A CN 202210413333 A CN202210413333 A CN 202210413333A CN 114773748 A CN114773748 A CN 114773748A
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Prior art keywords
pvc
aconitate
parts
resin
tributyl
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CN202210413333.1A
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Chinese (zh)
Inventor
蒋伟
闫建强
乔风臣
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Shandong Onetwo Polymer Materials Co ltd
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Shandong Onetwo Polymer Materials Co ltd
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Priority to CN202210413333.1A priority Critical patent/CN114773748A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions 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
    • C08L27/02Compositions 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
    • C08L27/04Compositions 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
    • C08L27/06Homopolymers or copolymers of vinyl chloride
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/06Biodegradable

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a composition containing tributyl aconitate and application thereof, which solve the technical problems of poor stability, easy stickiness, poor mold release, no aging resistance, easy yellowing and low migration resistance of citrate in the prior art, and comprise PVC resin, tributyl aconitate, epoxidized soybean oil, a viscosity reducer, a stabilizer and a mold release agent. The invention can be used in the field of preparation of children's utensils.

Description

Composition containing tributyl aconitate and application thereof
Technical Field
The invention relates to a composition and a preparation method and application thereof, in particular to a composition containing tributyl aconitate and application thereof.
Background
Tributyl citrate and acetyl tributyl citrate are biodegradable nontoxic environment-friendly plasticizers with large consumption in the current market, but have inevitable defects, such as poor processing stability, low aging resistance and easy yellowing, and PVC products have the tastes of easy volatilization, extreme nose choking and pungent throat in the plasticizing process of tributyl citrate and acetyl tributyl citrate, so that the use cost and the waste gas treatment cost of PVC product factories are increased.
Aconitum acid ester is obtained by removing one part of water from citrate, and can also be prepared by reacting aconitic acid with corresponding alcohol. In the processing process of plasticizing PVC products, the aconitate hardly has various defects of citrate, has good demoulding property and does not stick to a mould; the viscosity is low, the using amount of the viscosity reducer can be reduced, and even the viscosity reducer can not be used; the aging resistance is excellent, and is better than DOP, and no yellowing occurs; the migration resistance is better.
Disclosure of Invention
The invention aims to solve the technical problems of poor stability, easy stickiness, poor demoulding property, no ageing resistance, easy yellowing and low migration resistance of citric acid ester in the prior art, and provides a composition containing tributyl aconitate and application thereof, wherein the composition has the characteristics of no toxicity, environmental protection, biodegradability and the like which are the same as those of tributyl citrate, and the performance of the composition is far superior to that of the tributyl citrate.
Therefore, the invention provides a composition containing tributyl aconitate, which comprises the following components in parts by weight: 100 parts of PVC resin; 15-120 parts of tributyl aconitate; 0-5 parts of epoxidized soybean oil; 0-5 parts of a viscosity reducer; 0.5-2 parts of a stabilizer; 0-0.5 part of a release agent.
Preferably, the tributyl aconitate is trans-tributyl aconitate or trans-triisobutyl aconitate, and the weight parts of the tributyl aconitate and the trans-triisobutyl aconitate are 100-120 parts.
Preferably, the PVC resin contains the following components in parts by weight: 80-100 parts of PVC paste resin; 0-20 parts of PVC suspension resin.
Preferably, the polymerization degree of the PVC paste resin is 1200-1500; the polymerization degree of the PVC suspension resin is 900-1000.
Preferably, the viscosity reducer is 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate.
Preferably, the stabilizer is a liquid calcium zinc stabilizer.
Preferably, the epoxidized soybean oil has an epoxy value of 6.0 or greater.
Preferably, the release agent is methyl silicone oil.
The invention also provides application of the composition containing the tributyl aconitate in preparing children appliances, which is characterized by comprising the following steps: mixing tributyl aconitate, epoxidized soybean oil and a stabilizer, uniformly stirring, adding PVC resin, a viscosity reducer and a release agent, and uniformly stirring again to obtain a PVC paste; b: defoaming, namely performing negative pressure defoaming on the PVC paste prepared in the step A; c: c, putting the PVC paste prepared in the step B into a copper mould; d: heating, namely putting the copper mould in the step C into a rotary vinyl furnace for heating; e: d, cooling, namely cooling the copper mould heated in the step D by using circulating water to shape the PVC product; f: opening the mold, namely opening the mold of the tool prepared in the step E and taking out the tool; g: and F, spraying paint, namely spraying the PVC appliance taken out in the step F to the specified part by using environment-friendly water-based or oil appliance paint to obtain a finished product.
Preferably, in the step B, the defoaming condition is 0.09 to 0.095 MPa; in the step D, the heating condition is 250-300 ℃ for 5-8 min.
The invention has the following beneficial effects:
the composition containing the aconitate is used for the processing process of the PVC product for children, has stable performance, does not generate any unpleasant odor, has good handfeel, is not sticky and does not stick to a mold.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Mixing 30g of tributyl aconitate, 5g of epoxidized soybean oil and 1.5g of stabilizer, uniformly stirring, adding 80g of PVC paste resin, 20g of PVC suspension resin, 5g of viscosity reducer and 0.2g of release agent, and uniformly stirring again to obtain a PVC paste; defoaming the PVC paste under the condition of 0.09 Mpa; pouring the paste into a mold after defoaming; placing the mould into a rotary vinyl furnace, and baking for 6min at 280 ℃; taking out and cooling to shape the product, opening the mold and taking out, and spraying paint on the appointed part with environment-friendly paint to obtain a finished product.
Example 2
Mixing 40g of tributyl aconitate, 4.5g of epoxidized soybean oil and 1.5g of stabilizer, uniformly stirring, adding 95g of PVC paste resin, 5g of PVC suspension resin, 4.5g of viscosity reducer and 0.2g of release agent, and uniformly stirring again to obtain a PVC paste; defoaming the PVC paste under the condition of 0.091 Mpa; pouring the paste into a mold after defoaming; placing the mould into a rotary vinyl furnace, and baking for 6min at 280 ℃; taking out and cooling to shape the product, opening the mold and taking out, and spraying paint on the appointed part with environment-friendly paint to obtain a finished product.
Example 3
Mixing 50g of tributyl aconitate, 4g of epoxidized soybean oil and 1.5g of stabilizer, uniformly stirring, adding 100g of PVC paste resin, 4g of viscosity reducer and 0.25g of release agent, and uniformly stirring again to obtain a PVC paste; defoaming the PVC paste under the condition of 0.09 Mpa; after defoaming, pouring the paste into a mold; placing the mould into a rotary vinyl furnace, and baking for 6min at 280 ℃; taking out and cooling to shape the product, opening the mold and taking out, and spraying paint on the appointed part with environment-friendly paint to obtain a finished product.
Example 4
Mixing 60g of tributyl aconitate, 3.5g of epoxidized soybean oil and 1.5g of stabilizer, uniformly stirring, adding 80g of PVC paste resin, 20g of PVC suspension resin, 3.5g of viscosity reducer and 0.25g of release agent, and uniformly stirring again to obtain a PVC paste; defoaming the PVC paste under the condition of 0.09 Mpa; pouring the paste into a mold after defoaming; placing the mould into a rotary vinyl furnace, and baking for 6min at 280 ℃; taking out and cooling to shape the product, opening the mold and taking out, and spraying paint on the appointed part with environment-friendly paint to obtain a finished product.
Example 5
Mixing 70g of tributyl aconitate, 3g of epoxidized soybean oil and 1.5g of stabilizer, uniformly stirring, adding 95g of PVC paste resin, 5g of PVC suspension resin, 3g of viscosity reducer and 0.3g of release agent, and uniformly stirring again to obtain a PVC paste; defoaming the PVC paste under the condition of 0.091 Mpa; pouring the paste into a mold after defoaming; placing the mould into a rotary vinyl furnace, and baking for 6min at 280 ℃; taking out and cooling to shape the product, opening the mold and taking out, and spraying paint on the appointed part with environment-friendly paint to obtain a finished product.
Example 6
Mixing 80g of tributyl aconitate, 2.5g of epoxidized soybean oil and 1.5g of stabilizer, uniformly stirring, adding 100g of PVC paste resin, 2.5g of viscosity reducer and 0.3g of release agent, and uniformly stirring again to obtain a PVC paste; defoaming the PVC paste under the condition of 0.09 Mpa; pouring the paste into a mold after defoaming; placing the mould into a rotary vinyl furnace, and baking for 6min at 280 ℃; taking out, cooling, shaping the product, opening the die, taking out, and spraying the paint on the specified part with environment-friendly paint to obtain the finished product.
Example 7
Mixing 90g of tributyl aconitate, 2g of epoxidized soybean oil and 1.5g of stabilizer, uniformly stirring, adding 100g of PVC paste resin, 2g of viscosity reducer and 0.35g of release agent, and uniformly stirring again to obtain a PVC paste; defoaming the PVC paste under the condition of 0.09 Mpa; pouring the paste into a mold after defoaming; placing the mould into a rotary vinyl furnace, and baking for 6min at 280 ℃; taking out and cooling to shape the product, opening the mold and taking out, and spraying paint on the appointed part with environment-friendly paint to obtain a finished product.
Example 8
Mixing 100g of tributyl aconitate, 1.5g of epoxidized soybean oil and 1.5g of stabilizer, uniformly stirring, adding 95g of PVC paste resin, 5g of PVC suspension resin, 1g of viscosity reducer and 0.35g of mold release agent, and uniformly stirring again to obtain a PVC paste; defoaming the PVC paste under the condition of 0.09 Mpa; after defoaming, pouring the paste into a mold; placing the mould into a rotary vinyl furnace, and baking for 6min at 280 ℃; taking out, cooling, shaping the product, opening the die, taking out, and spraying the paint on the specified part with environment-friendly paint to obtain the finished product.
Example 9
Mixing 110g of tributyl aconitate, 1g of epoxidized soybean oil and 1.5g of stabilizer, uniformly stirring, adding 100g of PVC paste resin and 0.4g of release agent, and uniformly stirring again to obtain a PVC paste; defoaming the PVC paste under the condition of 0.091 Mpa; after defoaming, pouring the paste into a mold; placing the mould into a rotary vinyl furnace, and baking for 6min at 280 ℃; taking out, cooling, shaping the product, opening the die, taking out, and spraying the paint on the specified part with environment-friendly paint to obtain the finished product.
Example 10
Mixing 120g of tributyl aconitate, 0.5g of epoxidized soybean oil and 1.5g of stabilizer, uniformly stirring, adding 80g of PVC paste resin, 20g of PVC suspension resin and 0.4g of release agent, and uniformly stirring again to obtain a PVC paste; defoaming the PVC paste under the condition of 0.09 Mpa; pouring the paste into a mold after defoaming; placing the mould into a rotary vinyl furnace, and baking for 6min at 280 ℃; taking out and cooling to shape the product, opening the mold and taking out, and spraying paint on the appointed part with environment-friendly paint to obtain a finished product.
Example 11
Mixing 100g of triisobutyl aconitate, 1.5g of epoxidized soybean oil and 0.5g of stabilizer, uniformly stirring, adding 95g of PVC paste resin, 5g of PVC suspension resin and 1.5g of viscosity reducer, and uniformly stirring again to obtain a PVC paste; defoaming the PVC paste under the condition of 0.09 Mpa; after defoaming, pouring the paste into a mold; placing the mould into a rotary vinyl furnace, and baking for 6min at 280 ℃; taking out and cooling to shape the product, opening the mold and taking out, and spraying paint on the appointed part with environment-friendly paint to obtain a finished product.
Example 12
Mixing and uniformly stirring 110g of triisobutyl aconitate, 1.5g of epoxidized soybean oil and 0.5g of stabilizer, adding 95g of PVC paste resin, 5g of PVC suspension resin and 1.7g of viscosity reducer, and uniformly stirring again to obtain a PVC paste; defoaming the PVC paste under the condition of 0.09 Mpa; pouring the paste into a mold after defoaming; placing the mould into a rotary vinyl furnace, and baking for 6min at 280 ℃; taking out and cooling to shape the product, opening the mold and taking out, and spraying paint on the appointed part with environment-friendly paint to obtain a finished product.
Example 13
Mixing 100g of tributyl aconitate, 20g of triisobutyl aconitate and 2g of stabilizer, uniformly stirring, adding 80g of PVC paste resin, 20g of PVC suspension resin, 0.5g of viscosity reducer and 0.1g of mold release agent, and uniformly stirring again to obtain a PVC paste; defoaming the PVC paste under the condition of 0.09 Mpa; pouring the paste into a mold after defoaming; placing the mould into a rotary vinyl furnace, and baking for 6min at 280 ℃; taking out, cooling, shaping the product, opening the die, taking out, and spraying the paint on the specified part with environment-friendly paint to obtain the finished product.
Example 14
Mixing 110g of tributyl aconitate, 10g of triisobutyl aconitate and 2g of stabilizer, uniformly stirring, adding 90g of PVC paste resin, 10g of PVC suspension resin, 0.3g of viscosity reducer and 0.1g of release agent, and uniformly stirring again to obtain a PVC paste; defoaming the PVC paste under the condition of 0.09 Mpa; pouring the paste into a mold after defoaming; placing the mould into a rotary vinyl furnace, and baking for 6min at 280 ℃; taking out, cooling, shaping the product, opening the die, taking out, and spraying the paint on the specified part with environment-friendly paint to obtain the finished product.
Example 15
Mixing 60g of tributyl aconitate and 60g of triisobutyl aconitate with 2g of stabilizer, uniformly stirring, adding 100g of PVC paste, 1g of viscosity reducer and 0.15g of release agent, and uniformly stirring again to obtain a PVC paste; defoaming the PVC paste under the condition of 0.09 Mpa; after defoaming, pouring the paste into a mold; placing the mould into a rotary vinyl furnace, and baking for 6min at 280 ℃; taking out and cooling to shape the product, opening the mold and taking out, and spraying paint on the appointed part with environment-friendly paint to obtain a finished product.
Comparative example 1
Mixing 100g of tributyl citrate, 3g of epoxidized soybean oil and 1.5g of stabilizer, uniformly stirring, adding 95g of PVC paste resin, 5g of PVC suspension resin, 8g of viscosity reducer and 0.6g of mold release agent, and uniformly stirring again to obtain a PVC paste material; defoaming the PVC paste under the condition of 0.09 Mpa; after defoaming, pouring the paste into a mold; placing the mould into a rotary vinyl furnace, and baking for 6min at 280 ℃; taking out and cooling to shape the product, opening the mold and taking out, and spraying paint on the appointed part with environment-friendly paint to obtain a finished product.
Comparative example 2
Mixing 110g of tri-n-butyl citrate, 3g of epoxidized soybean oil and 1.5g of stabilizer, uniformly stirring, adding 100g of PVC paste resin, 7.5g of viscosity reducer and 0.6g of release agent, and uniformly stirring again to obtain a PVC paste; defoaming the PVC paste under the condition of 0.09 Mpa; pouring the paste into a mold after defoaming; placing the mould into a rotary vinyl furnace, and baking for 6min at 280 ℃; taking out, cooling, shaping the product, opening the die, taking out, and spraying the paint on the specified part with environment-friendly paint to obtain the finished product.
Table 1: comparison of Performance data for examples 1-15 and comparative examples 1-2
Figure BDA0003604612520000071
As shown in Table 1, the aconitate ester is stable in processing when used in PVC products for children (such as toys or other children products), does not generate any unpleasant odor, and has good hand feeling, no stickiness and no sticking to molds.
When triisobutyl aconitate is used completely, even no release agent is used, the PVC product can be easily released. From examples 13 to 15, it is understood that epoxidized soybean oil can be eliminated and the processing requirements can be satisfied by increasing the amount of the stabilizer by 0.5 part.
When all the aconitic acid tri-n-butyl ester is used, the dosage of the viscosity reducer can be reduced to zero, and the production and manufacturing cost of PVC products can be greatly reduced.
However, the above description is only exemplary of the present invention, and the scope of the present invention should not be limited thereby, and the replacement of the equivalent components or the equivalent changes and modifications made according to the protection scope of the present invention should be covered by the claims of the present invention.

Claims (10)

1. The composition containing tributyl aconitate is characterized by comprising the following components in parts by weight: 100 parts of PVC resin; 15-120 parts of tributyl aconitate; 0-5 parts of epoxidized soybean oil; 0-5 parts of a viscosity reducer; 0.5-2 parts of a stabilizer; 0-0.5 part of a release agent.
2. The composition containing tributyl aconitate according to claim 1, wherein the tributyl aconitate is trans-tributyl aconitate or trans-triisobutyl aconitate, and the weight part is 100-120 parts.
3. The composition containing tributyl aconitate according to claim 1, wherein the PVC resin contains the following components in parts by weight: 80-100 parts of PVC paste resin; 0-20 parts of PVC suspension resin.
4. The composition containing tributyl aconitate according to claim 1, wherein the polymerization degree of the PVC paste resin is 1200-1500; the polymerization degree of the PVC suspension resin is 900-1000.
5. The composition of claim 1 containing tributyl aconitate wherein the viscosity reducing agent is 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate.
6. The composition of claim 1 containing tributyl aconitate wherein the stabilizer is a liquid calcium zinc stabilizer.
7. The composition containing tributyl aconitate according to claim 1, wherein the epoxidized soybean oil has an epoxy value of 6.0 or more.
8. The composition of claim 1 comprising tributyl aconitate wherein the release agent is methyl silicone oil.
9. Use of a composition comprising tributyl aconitate according to claim 1 for the preparation of a children's utensil, characterized in that it comprises the following steps:
a, mixing tributyl aconitate, epoxidized soybean oil and a stabilizer, uniformly stirring, adding PVC resin, a viscosity reducer and a release agent, and uniformly stirring again to obtain a PVC paste;
b, defoaming, namely performing negative pressure defoaming on the PVC paste prepared in the step A;
c: c, putting the PVC paste prepared in the step B into a mold;
d: heating, namely heating the mould in the step C;
e: d, cooling, namely cooling the heated mould in the step D by using circulating water to shape the PVC product so as to obtain a tool;
f: opening the mold, namely opening the mold of the tool prepared in the step E and taking out the tool;
g: and F, spraying paint, namely spraying paint on the PVC appliance taken out in the step F to obtain a finished product.
10. The use of a composition containing tributyl aconitate according to claim 9 in the preparation of a children's utensil, wherein in the step B, the defoaming condition is 0.09Mpa to 0.095 Mpa; in the step D, the heating condition is 250-300 ℃ for 5-8 min.
CN202210413333.1A 2022-04-20 2022-04-20 Composition containing tributyl aconitate and application thereof Pending CN114773748A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024235233A1 (en) * 2023-05-15 2024-11-21 中国科学院青岛生物能源与过程研究所 Bio-based trans-aconitate, preparation method therefor and use thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070287781A1 (en) * 2006-06-08 2007-12-13 Oxeno Olefinchemie Gmbh Tripentyl citrates and their use
CN108409574A (en) * 2018-04-16 2018-08-17 山东万图高分子材料股份有限公司 A kind of citrate and its preparation method and application
CN113817223A (en) * 2021-08-30 2021-12-21 中国科学院青岛生物能源与过程研究所 Aconitate polyvinyl chloride plasticizer and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070287781A1 (en) * 2006-06-08 2007-12-13 Oxeno Olefinchemie Gmbh Tripentyl citrates and their use
CN108409574A (en) * 2018-04-16 2018-08-17 山东万图高分子材料股份有限公司 A kind of citrate and its preparation method and application
CN113817223A (en) * 2021-08-30 2021-12-21 中国科学院青岛生物能源与过程研究所 Aconitate polyvinyl chloride plasticizer and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024235233A1 (en) * 2023-05-15 2024-11-21 中国科学院青岛生物能源与过程研究所 Bio-based trans-aconitate, preparation method therefor and use thereof

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