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CN112280097A - Mixed plasticizer and preparation method thereof - Google Patents

Mixed plasticizer and preparation method thereof Download PDF

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Publication number
CN112280097A
CN112280097A CN202011123525.6A CN202011123525A CN112280097A CN 112280097 A CN112280097 A CN 112280097A CN 202011123525 A CN202011123525 A CN 202011123525A CN 112280097 A CN112280097 A CN 112280097A
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Prior art keywords
water
isobutyraldehyde
sodium hydroxide
reaction
catalyst
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Inventor
孔令航
杨涌波
孔晓伟
林显云
孙徽
贾帮乐
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ANHUI SHIHUA CHEMICAL CO LTD
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ANHUI SHIHUA CHEMICAL CO LTD
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016Plasticisers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/10Esters; Ether-esters
    • C08K5/101Esters; Ether-esters of monocarboxylic acids
    • 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

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention relates to the technical field of novel plasticizers, and particularly discloses a mixed plasticizer which comprises the following raw material components in percentage by weight: 32-48% of isobutyraldehyde, 6-10% of sodium hydroxide, 10-12% of water-carrying agent, 2-4% of catalyst and the balance of deionized water; the preparation method comprises the following steps: (1) raw material preparation, (2) aldol condensation reaction, (3) precedent reaction, (4) preparation of isobutyric acid, and (5) synthesis reaction. The invention overcomes the defects of the prior art, synthesizes the mixed plasticizer by taking isobutyraldehyde as a raw material to carry out aldol condensation, quaternionic reaction and synthesis reaction, has wide raw material source and low price, greatly reduces the cost, and has simple method and easy operation.

Description

Mixed plasticizer and preparation method thereof
Technical Field
The invention relates to the technical field of novel plasticizers, and particularly belongs to a mixed plasticizer.
Background
PVC is widely applied to various fields as an important engineering plastic. Due to the hard and brittle nature of pure PVC, a certain amount of plasticizer is often added to the PVC to lower the glass transition temperature and improve its processability. At present, common phthalate plasticizers are easy to migrate out of products, so that the common phthalate plasticizers are easy to threaten human health, are forbidden to be used in a plurality of fields by the European Union, and are gradually limited to be used in China at present. With the increasing strictness of environmental requirements, there is a need to find a sustainable environment-friendly plasticizer to replace the conventional phthalate plasticizer.
Disclosure of Invention
The invention aims to provide a mixed plasticizer, overcomes the defects of the prior art, synthesizes the mixed plasticizer by taking isobutyraldehyde as a raw material to carry out aldol condensation, quaternionic reaction and synthesis reaction, has wide raw material source and low price, greatly reduces the cost, and has simple method and easy operation.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a mixed plasticizer comprises the following raw material components in percentage by weight: 32-48% of isobutyraldehyde, 6-10% of sodium hydroxide, 10-12% of water-carrying agent, 2-4% of catalyst and the balance of deionized water.
Further, the material comprises the following raw materials in percentage by weight: isobutyraldehyde 32%, sodium hydroxide 6%, water-carrying agent 10%, catalyst 2% and deionized water 50%.
Further, the material comprises the following raw materials in percentage by weight: 40% of isobutyraldehyde, 8% of sodium hydroxide, 11% of water-carrying agent, 3% of catalyst and 38% of deionized water.
Further, the material comprises the following raw materials in percentage by weight: isobutyraldehyde 48%, sodium hydroxide 10%, water-carrying agent 12%, catalyst 4% and deionized water 26%.
Further, the water-carrying agent is any one of n-hexane, cyclohexane, petroleum ether and anisole.
Further, the catalyst is any one of terephthalic acid, thionyl oxalate and dinitrobenzoic acid.
A preparation method based on the mixed plasticizer is characterized in that isobutyraldehyde is used as a raw material, aldol condensation and quaternionic reaction are carried out, an intermediate product and sodium isobutyrate are collected, and the sodium isobutyrate is acidified and purified to obtain isobutyric acid; and reacting the isobutyric acid and the intermediate product under the conditions of a catalyst, a water-carrying agent and high temperature, and separating and purifying to obtain the environment-friendly plasticizer.
Further, the method comprises the following specific steps:
(1) preparing raw materials: weighing the raw materials according to the weight ratio of the raw materials, dividing sodium hydroxide into two parts according to the weight ratio of 1:2, respectively adding deionized water to prepare a 15% diluted sodium hydroxide aqueous solution and a 50% concentrated sodium hydroxide aqueous solution in parts by mass, and respectively sealing for later use;
(2) aldol condensation reaction: adding isobutyraldehyde into a reactor, slowly dropwise adding a 15% dilute sodium hydroxide aqueous solution into the isobutyraldehyde through a separating funnel, and violently stirring the isobutyraldehyde while dropwise adding until the reaction is complete;
(3) quaternary reaction: dropwise adding 50% concentrated sodium hydroxide aqueous solution into the reaction system in the step (2), raising the temperature to a certain temperature, and reacting under the condition of continuous stirring; after the reaction is finished, adding a proper amount of deionized water into the product for washing, separating a lower layer solution by using a separating funnel for later use, repeatedly washing the upper layer clear solution for 2-3 times by using water, and collecting a lower layer sodium isobutyrate solution; distilling the washed product, heating to 140 ℃ until no matter is distilled out, and standing the fraction to separate the upper unreacted isobutyraldehyde for recycling; then, collecting 105 ℃ fractions under the vacuum degree of 1.1kPa to obtain intermediate products;
(4) preparation of isobutyric acid: distilling and concentrating the sodium isobutyrate solution collected in the step (2), dropwise adding concentrated sulfuric acid into the sodium isobutyrate solution under stirring until the pH value is about 2.0, separating an upper organic layer, and distilling and purifying to obtain isobutyric acid;
(5) and (3) synthesis reaction: adding the intermediate product obtained in the step (2) and the isobutyric acid obtained in the step (3) into a reactor, adding a proper amount of a water-carrying agent and a catalyst, introducing argon gas for 30min, then putting the mixture into an oil bath pot, stirring and heating, observing the water outlet condition, starting to evaporate water when the internal temperature is about 130 ℃, then gradually heating, heating to 5 ℃ every half hour until the water outlet is complete, firstly pumping out the water-carrying agent and excessive unreacted isobutyric acid by using a circulating water type vacuum pump, cooling, filtering out the catalyst, washing by using a dilute sodium carbonate aqueous solution, carrying out water solubility, and then collecting 120 ℃ fractions under the vacuum degree of 1.1k Pa to obtain the mixed plasticizer.
Compared with the prior art, the invention has the following implementation effects:
according to the invention, isobutyraldehyde is used as a raw material to carry out aldol condensation, quaternionic reaction and synthesis reaction to synthesize the mixed plasticizer, the raw material source is wide, the price is low, the cost is greatly reduced, and the method is simple and easy to operate; the molecule of the mixed plasticizer contains an ester-based polar part and a nonpolar methyl structure, wherein the polar part enables the mixed plasticizer to be well compatible with PVC, and the nonpolar part enables resin molecules to be mutually separated, so that the intermolecular distance is increased, the intermolecular force is weakened, and the mixed plasticizer has a good plasticizing effect.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples, and any modification is within the scope of the present invention without departing from the spirit of the present invention.
Example 1
The embodiment discloses a mixed plasticizer, which comprises the following raw material components in percentage by weight: isobutyraldehyde 32%, sodium hydroxide 6%, water-carrying agent 10%, catalyst 2% and deionized water 50%; the water-carrying agent is any one of n-hexane, cyclohexane, petroleum ether and anisole; the catalyst is any one of terephthalic acid, cuprous oxalate and dinitrobenzoic acid.
The preparation method comprises the following steps:
(1) preparing raw materials: weighing the raw materials according to the weight ratio of the raw materials, dividing sodium hydroxide into two parts according to the weight ratio of 1:2, respectively adding deionized water to prepare a 15% diluted sodium hydroxide aqueous solution and a 50% concentrated sodium hydroxide aqueous solution in parts by mass, and respectively sealing for later use;
(2) aldol condensation reaction: adding isobutyraldehyde into a reactor, slowly dropwise adding a 15% dilute sodium hydroxide aqueous solution into the isobutyraldehyde through a separating funnel, and violently stirring the isobutyraldehyde while dropwise adding until the reaction is complete;
(3) quaternary reaction: dropwise adding 50% concentrated sodium hydroxide aqueous solution into the reaction system in the step (2), raising the temperature to a certain temperature, and reacting under the condition of continuous stirring; after the reaction is finished, adding a proper amount of deionized water into the product for washing, separating a lower layer solution by using a separating funnel for later use, repeatedly washing the upper layer clear solution for 2-3 times by using water, and collecting a lower layer sodium isobutyrate solution; distilling the washed product, heating to 140 ℃ until no matter is distilled out, and standing the fraction to separate the upper unreacted isobutyraldehyde for recycling; then, collecting 105 ℃ fractions under the vacuum degree of 1.1kPa to obtain intermediate products;
(4) preparation of isobutyric acid: distilling and concentrating the sodium isobutyrate solution collected in the step (2), dropwise adding concentrated sulfuric acid into the sodium isobutyrate solution under stirring until the pH value is about 2.0, separating an upper organic layer, and distilling and purifying to obtain isobutyric acid;
(5) and (3) synthesis reaction: adding the intermediate product obtained in the step (2) and the isobutyric acid obtained in the step (3) into a reactor, adding a proper amount of a water-carrying agent and a catalyst, introducing argon gas for 30min, then putting the mixture into an oil bath pot, stirring and heating, observing the water outlet condition, starting to evaporate water when the internal temperature is about 130 ℃, then gradually heating, heating to 5 ℃ every half hour until the water outlet is complete, firstly pumping out the water-carrying agent and excessive unreacted isobutyric acid by using a circulating water type vacuum pump, cooling, filtering out the catalyst, washing by using a dilute sodium carbonate aqueous solution, carrying out water solubility, and then collecting 120 ℃ fractions under the vacuum degree of 1.1k Pa to obtain the mixed plasticizer.
Example 2
The raw materials and preparation method of the mixed plasticizer disclosed in this example are substantially the same as those of the examples, except that: the mixed plasticizer comprises the following raw material components in percentage by weight: 40% of isobutyraldehyde, 8% of sodium hydroxide, 11% of water-carrying agent, 3% of catalyst and 38% of deionized water.
Example 3
The raw materials and preparation method of the mixed plasticizer disclosed in this example are substantially the same as those of the examples, except that: the mixed plasticizer comprises the following raw material components in percentage by weight: isobutyraldehyde 48%, sodium hydroxide 10%, water-carrying agent 12%, catalyst 4% and deionized water 26%.
Detection method
Respectively preparing a mixed plasticizer according to the raw material proportion and the preparation method of the embodiment 1-3, then mixing the plasticizer and PVC to prepare a film, and respectively adopting a pure PVC film without the plasticizer and a plasticizer of a certain company sold in the market as a control group 1 and a control group 2; the mechanical strength of the PVC films prepared in examples 1-3 and control groups 1-2 was measured, and the specific measurement results are shown in the following table:
Figure BDA0002732855730000061
the data in the table show that the mixed plasticizer obtained by the invention has better effect, can effectively improve the strength and toughness of PVC, and has better advance compared with the products sold in the market.
The foregoing is merely exemplary and illustrative of the present inventive concept and various modifications, additions and substitutions of similar embodiments may be made to the specific embodiments described by those skilled in the art without departing from the inventive concept or exceeding the scope of the claims as defined in the accompanying claims.

Claims (8)

1. A hybrid plasticizer characterized by: the composite material comprises the following raw materials in percentage by weight: 32-48% of isobutyraldehyde, 6-10% of sodium hydroxide, 10-12% of water-carrying agent, 2-4% of catalyst and the balance of deionized water.
2. A hybrid plasticizer according to claim 1, wherein: the composite material comprises the following raw materials in percentage by weight: isobutyraldehyde 32%, sodium hydroxide 6%, water-carrying agent 10%, catalyst 2% and deionized water 50%.
3. A hybrid plasticizer according to claim 1, wherein: the composite material comprises the following raw materials in percentage by weight: 40% of isobutyraldehyde, 8% of sodium hydroxide, 11% of water-carrying agent, 3% of catalyst and 38% of deionized water.
4. A hybrid plasticizer according to claim 1, wherein: the composite material comprises the following raw materials in percentage by weight: isobutyraldehyde 48%, sodium hydroxide 10%, water-carrying agent 12%, catalyst 4% and deionized water 26%.
5. A hybrid plasticizer according to claim 1, wherein: the water-carrying agent is any one of n-hexane, cyclohexane, petroleum ether and anisole.
6. A hybrid plasticizer according to claim 1, wherein: the catalyst is any one of terephthalic acid, cuprous oxalate and dinitrobenzoic acid.
7. A method for preparing a mixed type plasticizer according to any one of claims 1 to 6, wherein: taking isobutyraldehyde as a raw material, firstly carrying out aldol condensation and Quinozake reaction, collecting an intermediate product and sodium isobutyrate, acidifying the sodium isobutyrate, and purifying to obtain isobutyric acid; and reacting the isobutyric acid and the intermediate product under the conditions of a catalyst, a water-carrying agent and high temperature, and separating and purifying to obtain the environment-friendly plasticizer.
8. The method of preparing a hybrid plasticizer according to claim 7, wherein: the method comprises the following specific steps:
(1) preparing raw materials: weighing the raw materials according to the weight ratio of the raw materials, dividing sodium hydroxide into two parts according to the weight ratio of 1:2, respectively adding deionized water to prepare a 15% diluted sodium hydroxide aqueous solution and a 50% concentrated sodium hydroxide aqueous solution in parts by mass, and respectively sealing for later use;
(2) aldol condensation reaction: adding isobutyraldehyde into a reactor, slowly dropwise adding a 15% dilute sodium hydroxide aqueous solution into the isobutyraldehyde through a separating funnel, and violently stirring the isobutyraldehyde while dropwise adding until the reaction is complete;
(3) quaternary reaction: dropwise adding 50% concentrated sodium hydroxide aqueous solution into the reaction system in the step (2), raising the temperature to a certain temperature, and reacting under the condition of continuous stirring; after the reaction is finished, adding a proper amount of deionized water into the product for washing, separating a lower layer solution by using a separating funnel for later use, repeatedly washing the upper layer clear solution for 2-3 times by using water, and collecting a lower layer sodium isobutyrate solution; distilling the washed product, heating to 140 ℃ until no matter is distilled out, and standing the fraction to separate the upper unreacted isobutyraldehyde for recycling; then, collecting 105 ℃ fractions under the vacuum degree of 1.1kPa to obtain intermediate products;
(4) preparation of isobutyric acid: distilling and concentrating the sodium isobutyrate solution collected in the step (2), dropwise adding concentrated sulfuric acid into the sodium isobutyrate solution under stirring until the pH value is about 2.0, separating an upper organic layer, and distilling and purifying to obtain isobutyric acid;
(5) and (3) synthesis reaction: adding the intermediate product obtained in the step (2) and the isobutyric acid obtained in the step (3) into a reactor, adding a proper amount of a water-carrying agent and a catalyst, introducing argon gas for 30min, then putting the mixture into an oil bath pot, stirring and heating, observing the water outlet condition, starting to evaporate water when the internal temperature is about 130 ℃, then gradually heating, heating to 5 ℃ every half hour until the water outlet is complete, firstly pumping out the water-carrying agent and excessive unreacted isobutyric acid by using a circulating water type vacuum pump, cooling, filtering out the catalyst, washing by using a dilute sodium carbonate aqueous solution, carrying out water solubility, and then collecting 120 ℃ fractions under the vacuum degree of 1.1k Pa to obtain the mixed plasticizer.
CN202011123525.6A 2020-10-20 2020-10-20 Mixed plasticizer and preparation method thereof Pending CN112280097A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101863762A (en) * 2010-06-30 2010-10-20 江苏天音化工有限公司 Method for preparing 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate
CN104640829A (en) * 2012-10-29 2015-05-20 Oxea有限责任公司 The production method of neopentyl glycol
CN105566106A (en) * 2016-02-24 2016-05-11 广州联普新材料科技有限公司 Method for preparing 2, 2, 4-trimethyl-1, 3-pentanediol double isobutyric acid ester

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101863762A (en) * 2010-06-30 2010-10-20 江苏天音化工有限公司 Method for preparing 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate
CN104640829A (en) * 2012-10-29 2015-05-20 Oxea有限责任公司 The production method of neopentyl glycol
CN105566106A (en) * 2016-02-24 2016-05-11 广州联普新材料科技有限公司 Method for preparing 2, 2, 4-trimethyl-1, 3-pentanediol double isobutyric acid ester

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
高俊: "环保增塑剂2,2,4-1,3-戊二醇二异丁酸酯的合成与应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

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