CN115466586A - Castor oil modified degradable hot melt adhesive and preparation method thereof - Google Patents
Castor oil modified degradable hot melt adhesive and preparation method thereof Download PDFInfo
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- CN115466586A CN115466586A CN202211270573.7A CN202211270573A CN115466586A CN 115466586 A CN115466586 A CN 115466586A CN 202211270573 A CN202211270573 A CN 202211270573A CN 115466586 A CN115466586 A CN 115466586A
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- hot melt
- melt adhesive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
- C08G2170/20—Compositions for hot melt adhesives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a castor oil modified degradable hot melt adhesive, which comprises the following components in parts by mole: dibasic acid: 50-100, diol: 50-100, castor oil: 5 to 10, polylactic acid: 10-20, styrene ethyl alcohol: 5-10, diethylene glycol divinyl ether: 5 to 10. The mechanical property of the hot melt adhesive is improved on the premise of ensuring the degradation rate.
Description
Technical Field
The invention relates to the field of macromolecules, in particular to a castor oil modified degradable hot melt adhesive and a preparation method thereof.
Background
The hot melt adhesive is a common industrial adhesive, and along with the development of environmental protection career, polylactic acid type hot melt adhesives are more and more appeared. The polylactic acid hot melt adhesive has the characteristic of easy degradation, but the polylactic acid hot melt adhesive has poor mechanical strength.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the castor oil modified polylactic acid degradable hot melt adhesive with better mechanical property.
In order to achieve the purpose, the invention provides the following technical scheme:
a castor oil modified degradable hot melt adhesive,
comprises the following mol portions:
dibasic acid: 50 to 100
A dihydric alcohol: 50 to 100
Castor oil: 5 to 10
Polylactic acid: 10 to 20
Ethylene styrene alcohol: 5 to 10
Diethylene glycol divinyl ether: 5 to 10.
As a further improvement of the present invention,
the dibasic acid is at least one of adipic acid, pimelic acid and suberic acid.
As a further improvement of the present invention,
the dihydric alcohol is: at least one of butanediol, hexanediol, heptanediol, octanediol, nonanediol, and decanediol.
As a further improvement of the present invention,
the molecular weight of the polylactic acid is 5000-20000.
As another object of the present invention, there is provided a method for preparing a hot melt adhesive,
the method comprises the following steps: mixing castor oil, a catalyst A and a solvent, and then adding styrene-ethanol and ethylene-diethylene glycol for full mixing; reacting for 1-3 hours at 25 ℃ to obtain a reaction mixture A;
step two: mixing dibasic acid, dihydric alcohol and polylactic acid, adding a catalyst B, heating to 190-210 ℃, removing water generated in the reaction in vacuum, and reacting for 1-2 hours to obtain a reaction mixture B;
step three: and mixing the reaction mixture A and the reaction mixture B, heating to 40 ℃ for reaction for 1-2 hours, and then heating to 160-200 ℃ for continuous reaction for 1-3 hours to obtain the hot melt adhesive.
As a further improvement of the present invention,
the catalyst A is a mixture of toluenesulfonic acid and zinc acetate with the mass ratio of 2: 1.
As a further improvement of the present invention,
the dosage of the catalyst A is 1/300-1/500 of the mass of the castor oil.
As a further improvement of the present invention,
the solvent in the first step is dichloromethane.
As a further improvement of the present invention,
the catalyst B is tetrabutyl titanate.
As a further improvement of the present invention,
the dosage of the catalyst B is 0.02-0.1% of the weight of the dibasic acid.
In the invention, castor oil is mainly adopted to react with styrene-ethylene alcohol and diethylene glycol monovinyl ether, wherein the molecular formula of the styrene-ethylene alcohol is shown in the specification
The molecular formula of diethylene glycol monovinyl ether is
The molecular structures of the two substances belong to a structure with one end being a double bond and the other end being a hydroxyl group, and the double bond can react with the hydroxyl group under the action of the catalyst A to form a structure with the following molecular formula
The castor oil contains hydroxyl, the styrene-ethylene alcohol and the diethylene glycol monovinyl ether can react with the castor oil and are connected to a castor oil molecular chain besides reacting with each other, the addition of the diethylene glycol monovinyl ether is mainly used for increasing acetal groups on the molecular chain, so that the whole molecular chain can be hydrolyzed more quickly under acidic conditions, and the addition of the styrene-ethylene alcohol is mainly used for increasing the rigidity of the molecular chain. Thus, a castor oil modifier was obtained.
After the castor oil modifier is obtained, the castor oil modifier is polymerized together with dibasic acid, dihydric alcohol and polylactic acid, and one castor oil molecule is provided with three same branched chains, so that a finally obtained high molecular compound can form a three-dimensional network structure, and the integral mechanical property of the castor oil modifier is better.
Detailed Description
The first embodiment is as follows:
a castor oil modified degradable hot melt adhesive,
comprises the following mol portions:
1, 7-pimelic acid: 100 portions of
1, 6-hexanediol: 100 portions of
Castor oil: 5 portions of
Polylactic acid having a molecular weight of 10000: 10 portions of
Ethylene styrene alcohol: 5 portions of
Diethylene glycol monovinyl ether: 10 parts.
The method comprises the following steps: mixing castor oil, a catalyst A and a solvent, then adding styrene ethanol and ethylene diethylene glycol, and fully mixing; reacting for 1 hour at 25 ℃ to obtain a reaction mixture A;
step two: mixing 1, 7-pimelic acid, 1, 6-hexanediol and polylactic acid, adding a catalyst B, heating to 190 ℃, removing water generated by the reaction in vacuum, and reacting for 1 hour to obtain a reaction mixture B;
step three: and mixing the reaction mixture A and the reaction mixture B, heating to 40 ℃ for reaction for 1 hour, heating to 180 ℃ and continuing to react for 3 hours to obtain the hot melt adhesive.
The catalyst A is prepared from the following components in a mass ratio of 2:1, toluene sulfonic acid and zinc acetate.
The dosage of the catalyst A is 1/300 of the mass of the castor oil.
The solvent in the first step is dichloromethane.
The catalyst B is tetrabutyl titanate.
The dosage of the catalyst B is 0.1 percent of the mass of the dibasic acid.
Comparative example one:
the hot melt adhesive can be degraded,
comprises the following mol portions:
1, 7-pimelic acid: 100 portions of
1, 6-hexanediol: 100 portions of
Polylactic acid having a molecular weight of 10000: 10 portions of
Mixing 1, 7-pimelic acid, 1, 6-hexanediol and polylactic acid, adding a catalyst B, heating to 190 ℃, removing water generated by the reaction in vacuum, and reacting for 4 hours to obtain a hot melt adhesive;
the catalyst B is tetrabutyl titanate.
The dosage of the catalyst B is 0.1 percent of the mass of the dibasic acid.
Comparative example two:
a castor oil modified degradable hot melt adhesive,
comprises the following mol portions:
1, 7-pimelic acid: 100 portions of
1, 6-hexanediol: 100 portions of
Castor oil: 5 portions of
Polylactic acid having a molecular weight of 10000: 10 parts.
Mixing 1, 7-pimelic acid, 1, 6-hexanediol, polylactic acid and castor oil, adding a catalyst B, heating to 190 ℃, removing water generated in the reaction in vacuum, and reacting for 4 hours to obtain a hot melt adhesive;
the catalyst B is tetrabutyl titanate.
The dosage of the catalyst B is 0.1 percent of the mass of the dibasic acid.
Raw material table:
| name (R) | Manufacturer of the product |
| 1, 7-pimelic acid | SHANGHAI YUANYE BIOTECHNOLOGY Co.,Ltd. |
| 1, 6-hexanediol | SHANGHAI YUANYE BIOTECHNOLOGY Co.,Ltd. |
| Castor oil | SHANGHAI YUANYE BIOTECHNOLOGY Co.,Ltd. |
| Polylactic acid (molecular weight 10000) | SHANGHAI YUANYE BIOTECHNOLOGY Co.,Ltd. |
| Ethylene styrene alcohol | Hubei Xin Mingtai chemical Co., ltd |
| Diethylene glycol monovinyl ether | Hubei Xinming Titai chemical Co., ltd |
| P-toluenesulfonic acid | Shandongyukang chemical Co Ltd |
| Zinc acetate | SHANGHAI YUANYE BIOTECHNOLOGY Co.,Ltd. |
| Methylene dichloride | NANJING CHEMICAL REAGENT Co.,Ltd. |
| Tetrabutyl titanate | Shanghai-derived leaf biological familyTech Ltd |
And (3) detection:
peel strength test standard: GB/T11402-1989
Tensile Strength test method reference ASTM D897-2008 (R2016)
The melt-cross-linked samples prepared in the examples and comparative examples were subjected to a pH =7 and citric acid and trisodium citrate were formulated into a buffer solution red having a pH of 5.5, and the change was observed.
From the comparison of example one with comparative examples one and two, it can be seen that the peel strength is almost the same and normal use can be achieved. The tensile strength of the first embodiment and the second embodiment is obviously better than that of the first embodiment in terms of mechanical property, because the castor oil molecules are added to form a three-dimensional network structure, so that the mechanical property is enhanced. However, in water with pH =7, there is almost no difference in the degradation rate between the examples and the comparative examples, but under acidic conditions, the first example is significantly faster and becomes granular in only two hours, because the acetal group has higher computational sensitivity, so that the macromolecule in the first example is decomposed into smaller molecular segments in advance, and thus the degradation is realized more quickly.
In the invention, castor oil is mainly adopted to react with styrene-ethylene alcohol and diethylene glycol monovinyl ether, wherein the molecular formula of the styrene-ethylene alcohol is shown in the specification
Diethylene glycol monovinyl ether has a molecular formula of
The molecular structures of the two substances are both double bonds at one end and hydroxyl at the other end, and the double bonds are reacted under the action of the catalyst ACan react with hydroxyl to form a structure of the formula
The castor oil contains hydroxyl, the ethylene styrene alcohol and the diethylene glycol monovinyl ether can react with the castor oil and are connected with a castor oil molecular chain besides the mutual reaction, the addition of the diethylene glycol monovinyl ether is mainly used for increasing acetal groups on the molecular chain, so that the whole molecular chain can be hydrolyzed more quickly under the acidic condition, and the addition of the ethylene styrene alcohol is mainly used for increasing the rigidity of the molecular chain. Thus, a castor oil modifier was obtained. After the castor oil modifier is obtained, the castor oil modifier is polymerized together with dibasic acid, dihydric alcohol and polylactic acid, and one castor oil molecule is provided with three same branched chains, so that a three-dimensional network structure can be formed by a finally obtained high molecular compound, the integral mechanical property of the castor oil modifier is better, and meanwhile, in the degradation process, due to the existence of an acetal group, molecular chains formed by the castor oil molecule and the dibasic acid, the dihydric alcohol and the polylactic acid can be quickly disconnected after the hydrolysis, so that the molecular weight is quickly reduced, the integral degradation rate cannot be influenced, the degradation rate is accelerated to a certain extent, and the mechanical property of the hot melt adhesive is improved on the premise of ensuring the degradation rate.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (10)
1. The castor oil modified degradable hot melt adhesive is characterized in that:
comprises the following mol portions:
dibasic acid: 50 to 100
Glycol: 50 to 100
Castor oil: 5 to 10
Polylactic acid: 10 to 20
Ethylene styrene alcohol: 5 to 10
Diethylene glycol monovinyl ether: 5 to 10.
2. The castor oil modified degradable hot melt adhesive of claim 1, wherein:
the dibasic acid is at least one of adipic acid, pimelic acid and suberic acid.
3. The castor oil modified degradable hot melt adhesive as claimed in claim 1, wherein:
the dihydric alcohol is: at least one of butanediol, hexanediol, heptanediol, octanediol, nonanediol, and decanediol.
4. The castor oil modified degradable hot melt adhesive of claim 1, wherein:
the molecular weight of the polylactic acid is 5000-20000.
5. The method for preparing a hot melt adhesive according to any one of claims 1 to 4, wherein:
the method comprises the following steps: mixing castor oil, a catalyst A and a solvent, and then adding styrene-ethanol and ethylene-diethylene glycol for full mixing; reacting for 1-3 hours at 25 ℃ to obtain a reaction mixture A;
step two: mixing dibasic acid, dihydric alcohol and polylactic acid, adding a catalyst B, heating to 190-210 ℃, removing water generated in the reaction in vacuum, and reacting for 1-2 hours to obtain a reaction mixture B;
step three: and mixing the reaction mixture A and the reaction mixture B, heating to 40 ℃ for reaction for 1-2 hours, and then heating to 160-200 ℃ for continuous reaction for 1-3 hours to obtain the hot melt adhesive.
6. The method for preparing hot melt adhesive according to claim 5, wherein:
the catalyst A is a mixture of toluenesulfonic acid and zinc acetate with the mass ratio of 2: 1.
7. The method for preparing hot melt adhesive according to claim 5, wherein:
the dosage of the catalyst A is 1/300-1/500 of the mass of the castor oil.
8. The method for preparing hot melt adhesive according to claim 5, wherein:
the solvent in the first step is dichloromethane.
9. The method for preparing a hot melt adhesive according to claim 5, wherein:
the catalyst B is tetrabutyl titanate.
10. The method for preparing hot melt adhesive according to claim 5, wherein:
the dosage of the catalyst B is 0.02-0.1% of the weight of the dibasic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211270573.7A CN115466586A (en) | 2022-10-17 | 2022-10-17 | Castor oil modified degradable hot melt adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211270573.7A CN115466586A (en) | 2022-10-17 | 2022-10-17 | Castor oil modified degradable hot melt adhesive and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115466586A true CN115466586A (en) | 2022-12-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211270573.7A Pending CN115466586A (en) | 2022-10-17 | 2022-10-17 | Castor oil modified degradable hot melt adhesive and preparation method thereof |
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| Country | Link |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004256642A (en) * | 2003-02-25 | 2004-09-16 | Japan Vam & Poval Co Ltd | Hot-melt adhesive |
| CN111978610A (en) * | 2020-09-04 | 2020-11-24 | 浙江中瑞橡胶高分子材料股份有限公司 | Bio-based modified rubber and preparation method thereof |
| CN112226191A (en) * | 2020-08-24 | 2021-01-15 | 江苏美境新材料有限公司 | Biodegradable adhesive and preparation method thereof |
-
2022
- 2022-10-17 CN CN202211270573.7A patent/CN115466586A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004256642A (en) * | 2003-02-25 | 2004-09-16 | Japan Vam & Poval Co Ltd | Hot-melt adhesive |
| CN112226191A (en) * | 2020-08-24 | 2021-01-15 | 江苏美境新材料有限公司 | Biodegradable adhesive and preparation method thereof |
| CN111978610A (en) * | 2020-09-04 | 2020-11-24 | 浙江中瑞橡胶高分子材料股份有限公司 | Bio-based modified rubber and preparation method thereof |
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