CN115073889A - High polymer material with good water retention and preparation method thereof - Google Patents

High polymer material with good water retention and preparation method thereof Download PDF

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CN115073889A
CN115073889A CN202110897005.9A CN202110897005A CN115073889A CN 115073889 A CN115073889 A CN 115073889A CN 202110897005 A CN202110897005 A CN 202110897005A CN 115073889 A CN115073889 A CN 115073889A
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component
polymer material
water retention
high polymer
good water
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贾雷
高鹏娜
马占
杨世美
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Shandong Ruian Biotechnology Co ltd
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Jiangsu Ruian Applied Biotechnology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16Dicarboxylic acids and dihydroxy compounds
    • C08G63/18Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181Acids containing aromatic rings
    • C08G63/183Terephthalic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66Polyesters containing oxygen in the form of ether groups
    • C08G63/668Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66Polyesters containing oxygen in the form of ether groups
    • C08G63/668Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672Dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2445/00Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
    • 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
    • C08K5/16Nitrogen-containing compounds
    • C08K5/29Compounds containing one or more carbon-to-nitrogen double bonds
    • 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
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • C08K5/521Esters of phosphoric acids, e.g. of H3PO4

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a high polymer material with good water retention, which comprises, by weight, 10-30 parts of a first component, 15-25 parts of a second component, 1.25-8.25 parts of a third component, 1-5 parts of a catalyst, 0.05-3 parts of a heat stabilizer and 1-3 parts of a tackifier. The high polymer material with good water retention property has good biodegradability, can realize the degradation of a film under specific environmental humidity and illumination after being applied to an agricultural film for a certain service life, cannot cause white pollution to the environment, and can greatly improve the degradable tensile strength through the optimized types and the use amount of the alkoxy branched chain alcohol as a raw material for preparation, so that the high polymer material has good mechanical strength.

Description

High polymer material with good water retention and preparation method thereof
Technical Field
The invention relates to a high polymer material with good water retention and a preparation method thereof, and mainly relates to the field of high polymer compound compositions.
Background
The production of polyester products brings great convenience to human life, but the environmental problem of white pollution is followed, and how to prepare polyester products with good degradation effect is a goal which is continuously pursued by scientists. The PBAT material is a material with better degradation effect, and the selection of the preparation raw materials can influence the tensile strength and the thermal stability of the PBAT in the process of producing the PBAT material. Patent CN201910763669.9 selects glycerol, ethylene glycol and sorbitol as plasticizers, and because of the low boiling point in the process of preparing PBAT, they are easy to be extracted along with the process of pressure reduction, and thus the effect cannot be completely realized. Patent CN202110054292.7 enhances the branching degree of polyester material by adding polyether, but it needs to use larger amount of polyether to achieve better branching effect and also causes the thermal stability of polyester to decrease.
Disclosure of Invention
In order to improve the thermal stability of the polyester film and obtain a product with good mechanical property, the first aspect of the invention provides a high polymer material with good water-retaining property, and the preparation raw materials comprise, by weight, 10-30 parts of a first component, 15-25 parts of a second component, 1.25-8.25 parts of a third component, 1-5 parts of a catalyst, 0.05-3 parts of a heat stabilizer and 1-3 parts of a tackifier.
As a preferred embodiment, the first component is selected from one or a combination of more of C2-C13 alkyl dibasic acid and cycloalkyl dibasic acid.
As a preferred embodiment, the cycloalkyl dibasic acid includes an aliphatic dibasic acid and an aromatic dibasic acid.
As a preferred embodiment, the molar ratio of the aliphatic dibasic acid to the aromatic dibasic acid is 1: (1.01-1.5).
As a preferred embodiment, the aromatic dibasic acid is selected from one or more of terephthalic acid, isophthalic acid and phthalic acid.
As a preferred embodiment, the aliphatic dibasic acid is selected from one or more of succinic acid, glutaric acid, adipic acid pimelic acid, suberic acid, azelaic acid, sebacic acid, and malic acid.
As a preferred embodiment, the second component is selected from one or a combination of several of C2-C13 alkyl diol and cycloalkyl diol.
As a preferred embodiment, the second component is selected from one or a combination of several of neopentyl glycol, 2-methyl-1, 3-propanediol, 1, 3-butanediol, 3-methyl-1, 5-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 2, 4-trimethyl-1, 3-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2-ethyl-1, 3-hexanediol, 2-methyl-1, 8-octanediol, dimer diol, hydroxypivalyl hydroxypivalate, dipropylene glycol, 1, 4-butanediol.
As a preferred embodiment, the third component is selected from one or more of C1-C9 alkoxy branched alcohols.
As a preferable embodiment, the C1-C18 alkoxy branched alcohol is selected from one or a combination of several of ethoxylated glycerin, propoxylated glycerin, ethoxylated trimethylolpropane, propoxylated trimethylolpropane and stearic glycerol.
As a preferred embodiment, the number of alkoxylated units in the alkoxy branched alcohol is 9 or less.
In a preferred embodiment, the alkoxylated branched alcohol is present in an amount of 0.05 to 0.15% by mass based on the total preparation starting materials.
In the experimental process, the applicant finds that the tensile strength of the biodegradable copolyester can be improved by adopting the alkoxylated branched alcohol, and the biodegradable copolyester has better thermal stability. The possible reasons for guessing are: the introduction of the alkoxylated branched alcohol can improve the branching degree of the main chain of the degradable polyester, increase the branching degree of the degradable polyester and enable the interior of the degradable polyester to form a stable cross-linked network, so that the tensile strength of the degradable polyester is improved, the introduction of the alkoxylated branched alcohol with the number of the alkoxylated units being less than or equal to 9 can improve the boiling point of the alkoxylated branched alcohol, prevent the alkoxylated branched alcohol from being extracted in the later vacuum-pumping process, and enable the alkoxylated branched alcohol to be introduced into the branched chain of the degradable polyester as much as possible. The addition of 0.05-0.15% by mass of the alkoxylated branched alcohol can improve the tensile strength of the degradable polyester without causing the reduction of the thermal stability of the degradable polyester.
In a preferred embodiment, the catalyst is selected from one or more of tetraisopropyl titanate, tetrabutyl titanate, zirconium alkoxide, tin alkoxide and acetate compounds.
In a preferred embodiment, the heat stabilizer is selected from one or more of phosphate, phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate and dipotassium hydrogen phosphate.
As a preferred embodiment, the tackifier is selected from one or a combination of several of petroleum resin, rosin resin, terpene resin and isocyanate.
As a preferred embodiment, the tackifier is a combination of a terpene resin and an isocyanate.
As a preferred embodiment, the weight ratio of the terpene resin and the isocyanate is 1: (1-2).
The applicant found during the course of the experiments that the tackifier was selected from the combination of terpene resin and isocyanate, and the weight ratio was 1: (1-2), the tensile properties can be further improved, and the terpene resin and the isocyanate can increase the branching degree of the degradable ester chain, promote the formation of a more stable cross-linked network, and further improve the mechanical strength.
The second aspect of the present invention provides a method for preparing a polymer material having a good water-retaining property, comprising the steps of:
(1) sequentially adding the first component, the second component, the third component and the catalyst into a reaction kettle, introducing argon, heating to 190-;
(2) continuously heating to 250 ℃ and 260 ℃, decompressing to 3-5kPa, and reacting for 1-2 h;
(3) adding a catalyst and a heat stabilizer, continuously reducing the pressure to 0.05-0.2kPa, and reacting for 1.5-3 h;
(4) adding the tackifier, mixing and stirring, transferring the obtained mixed product to an extruder, and extruding a film to obtain the adhesive.
As a preferred embodiment, the weight ratio of the catalyst added in step 1 and step 3 is 1: (0.1-1).
Further preferably, the weight ratio of the catalyst added in step 1 and step 3 is 1: (0.3-0.5).
Compared with the prior art, the invention has the following beneficial effects:
(1) the high polymer material with good water retention property has good biodegradability, can realize the degradation of a film under the specific environment humidity and illumination after being applied to an agricultural film to complete a certain service life, cannot cause white pollution to the environment, is particularly suitable for being applied to the agricultural film production, has strong hydrophobicity, has good water retention effect on plants, and is beneficial to the growth of young plants.
(2) The high polymer material with good water retention property can greatly improve the degradable tensile strength by optimally preparing the type and the using amount of the alkoxy branched chain alcohol serving as the raw material, so that the high polymer material has better mechanical strength.
(3) The polymer material with good water retention property of the invention has good transparency and enough thermal stability through the types and adding amounts of the catalyst, the heat stabilizer and the tackifier which are preferably used.
Detailed Description
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Example 1
The high polymer material with good water retention property comprises 20 parts by weight of a first component, 20 parts by weight of a second component, 3.55 parts by weight of a third component, 3 parts by weight of a catalyst, 1.55 parts by weight of a heat stabilizer and 2 parts by weight of a tackifier.
The first component is a combination of adipic acid and terephthalic acid in a weight ratio of 1: 1.2.
the second component is 1, 4-butanediol.
The third component is stearic acid glycerol which is purchased from Hubei Xinkang pharmaceutical chemical industry Co.
The catalyst is tetraisopropyl titanate.
The heat stabilizer is butyl phosphate.
The tackifier is terpene resin and isocyanate, and the weight ratio of the terpene resin to the isocyanate is 1: 1, the terpene resin is purchased from Shenzhen Jitian chemical industry Co., Ltd, the model is BT28D, and the isocyanate is purchased from Tantaowawa, the model is PM-200.
A preparation method of a high polymer material with good water retention property comprises the following steps:
(1) sequentially adding the first component, the second component, the third component and the catalyst into a reaction kettle, introducing argon, heating to 210 ℃, and reacting for 3 hours;
(2) continuously heating to 255 ℃, decompressing to 4kPa, and reacting for 1.5 h;
(3) adding a catalyst and a heat stabilizer, continuously reducing the pressure to 0.15kPa, and reacting for 2 hours;
(4) adding the tackifier, mixing and stirring, transferring the obtained mixed product to an extruder, and extruding a film to obtain the adhesive.
The weight ratio of the catalyst added in the step 1 and the step 3 is 1: 0.4.
example 2
The high polymer material with good water retention property comprises 15 parts by weight of a first component, 15 parts by weight of a second component, 2.25 parts by weight of a third component, 2 parts by weight of a catalyst, 1 part by weight of a heat stabilizer and 1.25 parts by weight of a tackifier.
The first component is a combination of adipic acid and terephthalic acid in a weight ratio of 1: 1.12.
the second component is 1, 4-butanediol and neopentyl glycol, and the weight ratio is 9: 1.
the third component is propoxylated glycerin which is purchased from Nantong Chen Runji chemical Co.
The catalyst is tetraisopropyl titanate.
The heat stabilizer is butyl phosphate.
The tackifier is terpene resin and isocyanate, and the weight ratio of the terpene resin to the isocyanate is 1: 1.5, the terpene resin is purchased from Shenzhen Jitian chemical Co., Ltd, the model is BT28D, the isocyanate is purchased from Taiwan tobacco, and the model is PM-200.
A preparation method of a high polymer material with good water retention property comprises the following steps:
(1) sequentially adding the first component, the second component, the third component and the catalyst into a reaction kettle, introducing argon, heating to 200 ℃, and reacting for 3.5 hours;
(2) continuously heating to 250 ℃, decompressing to 5kPa, and reacting for 2 h;
(3) adding a catalyst and a heat stabilizer, continuously reducing the pressure to 0.1kPa, and reacting for 3 hours;
(4) adding the tackifier, mixing and stirring, transferring the obtained mixed product to an extruder, and extruding a film to obtain the adhesive.
Example 3
The specific steps of a high polymer material with good water retention property and a preparation method thereof are the same as example 1, and the difference is that the third component is decyloxylated trimethylolpropane.
Example 4
The specific steps of a high polymer material with good water retention property and a preparation method thereof are the same as those of example 1, and the difference is that the third component is glycerol.
Example 5
The specific steps of a high polymer material with good water retention property and a preparation method thereof are the same as those of example 1, and the difference is that the mass fraction of the alkoxylated branched alcohol in the total preparation raw materials is 0.03%.
Performance testing
1. Tensile strength: the tensile strength of the films prepared was tested according to the GB 13022-1991 standard.
2. Elongation at break: the elongation at break of the films prepared was tested according to the GB 13022-1991 standard.
3. Hydrophobicity test: and testing the hydrophobicity of the prepared film according to the GB/T20000.2-2009 standard, and testing the contact angle of the surface of the film and water.
Examples 1-5 were tested according to the criteria described above and the results are shown in table 1.
TABLE 1
Figure BDA0003198378570000051
Figure BDA0003198378570000061

Claims (10)

1. The high polymer material with good water retention is characterized in that the preparation raw materials comprise, by weight, 10-30 parts of a first component, 15-25 parts of a second component, 1.25-8.25 parts of a third component, 1-5 parts of a catalyst, 0.05-3 parts of a heat stabilizer and 1-3 parts of a tackifier;
the first component is a dibasic acid, the second component is a glycol, and the third component is an alkoxy alcohol.
2. The high polymer material with good water retention property according to claim 1, wherein the first component is selected from one or a combination of C2-C13 alkyl dibasic acid and cycloalkyl dibasic acid.
3. The high polymer material with good water retention according to claim 2, wherein the naphthenic dibasic acid comprises aliphatic dibasic acid and aromatic dibasic acid.
4. The high polymer material with good water retention according to claim 3, wherein the molar ratio of the aliphatic dibasic acid to the aromatic dibasic acid is 1: (1.01-1.5).
5. The high polymer material with good water retention property according to claim 1, wherein the second component is selected from one or more of C2-C13 alkyl diol and cycloalkyl diol.
6. The high polymer material with good water retention according to claim 1, wherein the second component is selected from one or more of neopentyl glycol, 2-methyl-1, 3-propanediol, 1, 3-butanediol, 3-methyl-1, 5-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 2, 4-trimethyl-1, 3-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2-ethyl-1, 3-hexanediol, 2-methyl-1, 8-octanediol, dimer diol, hydroxypivalate, dipropylene glycol, and 1, 4-butanediol.
7. The high polymer material with good water retention property according to claim 1, wherein the third component is selected from one or more of C2-C18 alkoxy branched alcohols.
8. The high polymer material with good water retention according to claim 4, wherein the C1-C9 alkoxy branched alcohol is selected from one or more of ethoxylated glycerol, propoxylated glycerol, ethoxylated trimethylolpropane and propoxylated trimethylolpropane.
9. The high polymer material with good water retention according to claim 1, wherein the catalyst is selected from one or a combination of more of tetraisopropyl titanate, tetrabutyl titanate, zirconium alkoxide, tin alkoxide, and acetate compounds.
10. A method for preparing a polymer material with good water retention according to any one of claims 1 to 9, comprising the steps of:
(1) sequentially adding the first component, the second component, the third component and the catalyst into a reaction kettle, introducing argon, heating to 190-;
(2) continuously heating to 250 ℃ and 260 ℃, decompressing to 3-5kPa, and reacting for 1-2 h;
(3) adding a catalyst and a heat stabilizer, continuously reducing the pressure to 0.05-0.2kPa, and reacting for 1.5-3 h;
(4) adding tackifier, mixing and stirring, transferring the obtained mixed product to an extruder, and extruding the film to obtain the product.
CN202110897005.9A 2021-08-05 2021-08-05 High polymer material with good water retention and preparation method thereof Pending CN115073889A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1826366A (en) * 2003-05-21 2006-08-30 三菱化学株式会社 Aliphatic polyester and process for production thereof
CN111892701A (en) * 2020-08-11 2020-11-06 广州德恒致远科技有限公司 Biodegradable copolyester and preparation method thereof
CN112521727A (en) * 2019-09-17 2021-03-19 中国石油化工股份有限公司 High-strength ultrathin biodegradable film and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1826366A (en) * 2003-05-21 2006-08-30 三菱化学株式会社 Aliphatic polyester and process for production thereof
CN112521727A (en) * 2019-09-17 2021-03-19 中国石油化工股份有限公司 High-strength ultrathin biodegradable film and preparation method thereof
CN111892701A (en) * 2020-08-11 2020-11-06 广州德恒致远科技有限公司 Biodegradable copolyester and preparation method thereof

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