CN112795362B - Ether modified reinforced hot melt adhesive - Google Patents
Ether modified reinforced hot melt adhesive Download PDFInfo
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- CN112795362B CN112795362B CN202011643914.1A CN202011643914A CN112795362B CN 112795362 B CN112795362 B CN 112795362B CN 202011643914 A CN202011643914 A CN 202011643914A CN 112795362 B CN112795362 B CN 112795362B
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- acid
- 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
- C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
- C09J177/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Polyamides (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses an ether modified reinforced hot melt adhesive, which comprises the following components in parts by mole: acid chloride-based compound: 1-2 parts of diamine: 20-30 parts of a dibasic acid: 20-30 parts of dihydric alcohol: 2-10 parts of diethylene glycol monovinyl ether: 1-5, the molecular structure is changed in the polymerization stage, so that the flexibility of the molecules of the obtained hot melt adhesive is improved due to the ether bond at the rear end, and meanwhile, oxygen atoms form a common electron pair with other carbon atoms, so that the bonding capacity of the hot melt adhesive is improved. And in addition, double bonds are introduced in the addition of acryloyl chloride, so that more possibility is provided for later modification of the hot melt adhesive, and the double bonds are easier to crosslink under the initiation of an initiator in the later modification process.
Description
Technical Field
The invention relates to the field of macromolecules, in particular to an ether modified reinforced hot melt adhesive.
Background
The Hot melt adhesive (English name: Hot Glue) is a plastic adhesive, the physical state of which changes with the temperature within a certain temperature range, but the chemical property is not changed, and the Hot melt adhesive is nontoxic and tasteless, and belongs to an environment-friendly chemical product.
In the prior art, the hot melt adhesive usually adopts a polyamide material as a main body of the hot melt adhesive, and ethers are modified, but in the modification process, the polyamide material is usually simply blended and compounded, and the modification is not carried out at the polymerization angle, so that the product performance is unstable.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an ether modified reinforced hot melt adhesive.
In order to achieve the purpose, the invention provides the following technical scheme:
ether modified reinforced hot melt adhesive
Comprises the following components in parts by mole:
acid chloride-based compound: 1 to 2 portions of
Diamine (b): 20 to 30 portions of
Dibasic acid: 20 to 30 portions of
A dihydric alcohol: 2 to 10 portions of
Diethylene glycol monovinyl ether: 1-5 parts.
As a further improvement of the present invention,
the acyl chloride-based compound is at least one of acryloyl chloride, methacryloyl chloride and butenoyl chloride.
As a further improvement of the present invention,
the diamine is at least one of ethylenediamine, propylenediamine, butanediamine, pentanediamine, hexanediamine, decanediamine, dodecanediamine, 2, 3-dimethylbutanediamine, 2-methylpentanediamine, 2-hexanediamine and 2, 2, 4-methylhexanediamine.
As a further improvement of the present invention,
the dibasic acid is at least one of succinic acid, glutaric acid, adipic acid, 2-methyl adipic acid, 1, 2-dimethyl adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid.
As a further improvement of the present invention,
the dihydric alcohol is at least one of ethylene glycol, propylene glycol, butanediol and pentanediol.
As a further improvement of the present invention,
the preparation method comprises the following steps:
the method comprises the following steps: adding dibasic acid and diamine into a reaction kettle, heating to 100-130 ℃, and preserving heat for 1 hour;
step two: continuously heating to 200-230 ℃ for continuous reaction for 1 hour, adding excessive dihydric alcohol for end capping, reacting for 0.5-1 hour at 200-230 ℃, and then vacuumizing at 230-270 ℃ with the vacuum degree of 0.08-0.1MPa to obtain a polymer;
step three: at room temperature, adding organic weak base and a catalyst into the polymer, then adding an acyl chloride compound and diethylene glycol monovinyl ether, and reacting for 10-15 hours at room temperature;
step four: and preserving the temperature to 20-30 ℃, and reacting for 10-20 hours to obtain the hot melt adhesive.
As a further improvement of the present invention,
the organic weak base is triethylamine, and the using amount of the organic weak base is 1-2 parts by mole;
the catalyst is p-toluenesulfonic acid, and the using amount is 0.05-0.1 part by mole;
the organic tin is stannous octoate, and the using amount is 0.01-0.05 parts by mole.
As a further improvement of the present invention,
the first step, the second step and the third step are carried out under the protection of nitrogen.
Wherein, in the process of ether modification, the reaction equation is as follows:
reaction 1:
reaction 2:
the invention has the advantages that the main body of the hot melt adhesive is mainly reacted by diamine and dibasic acid to obtain a polyamide body, then excessive dihydric alcohol is added for end capping to obtain a polymer with two ends provided with hydroxyl groups, then an acyl chloride compound is polymerized on the hydroxyl group at one end of the polymer under the catalysis of organic weak base and a catalyst, diethylene glycol monovinyl ether is added, one end of the diethylene glycol monovinyl ether can be polymerized on the hydroxyl group at one end of the polymer, the other end of the diethylene glycol monovinyl ether is also provided with the hydroxyl group, the diethylene glycol monovinyl ether can be continuously polymerized to obtain the ether modified polyamide body, the molecular structure is changed in the polymerization stage, the flexibility of the obtained hot melt adhesive is improved due to the ether bond at the rear end, meanwhile, the oxygen atom has lone pair electrons and other carbons form a common electron pair, the bonding capacity of the hot melt adhesive is increased. And in addition, double bonds are introduced in the addition of acryloyl chloride, so that more possibility is provided for the modification of the hot melt adhesive in the later period, and the double bonds are easier to crosslink under the initiation of an initiator in the later modification process.
Detailed Description
Example (b):
taking:
acryloyl chloride: 9g
Decamethylenediamine: 500g
Adipic acid: 430g
Ethylene glycol: 18g of
Diethylene glycol monovinyl ether: 40g of the total weight of the mixture;
organic weak base: triethylamine: 10.1g
Catalyst: p-toluenesulfonic acid: 0.9 g;
the preparation method comprises the following steps:
the method comprises the following steps: adding dibasic acid and diamine into a reaction kettle, heating to 120 ℃, and preserving heat for 1 hour;
step two: continuously heating to 230 ℃ and continuously reacting for 1 hour, adding excessive dihydric alcohol to perform end capping, and reacting for 1 hour at 250 ℃ and the vacuum degree of 0.09MPa to obtain a polymer;
step three: adding organic weak base and a catalyst into the polymer at room temperature, then adding an acyl chloride compound and diethylene glycol monovinyl ether, and reacting for 10 hours at room temperature;
step four: preserving the temperature to 30 ℃, and reacting for 10 hours to obtain the hot melt adhesive.
The first step, the second step and the third step are carried out under the protection of nitrogen.
Comparative example:
taking:
decamethylenediamine: 500g
Adipic acid: 430g
Ethylene glycol: 18g of
The preparation method comprises the following steps:
the method comprises the following steps: adding dibasic acid and diamine into a reaction kettle, heating to 120 ℃, and preserving heat for 1 hour;
step two: continuously heating to 230 ℃ and continuously reacting for 1 hour, adding excessive dihydric alcohol to perform end capping, reacting for 1 hour at 260 ℃ and reacting for 1 hour at the vacuum degree of 0.1MPa to obtain a polymer;
step three: reacting at room temperature for 10-15 hours;
step four: keeping the temperature to 30 ℃, and reacting for 10 hours to obtain the hot melt adhesive.
The first step, the second step and the third step are carried out under the protection of nitrogen.
The examples and comparative examples were tested:
the peel strength was measured according to GB/T2790 with test parameters of 30kg, 5cm and 120 s.
Tensile strength test method was performed in accordance with ASTM D897-2008 (R2016).
The melting point was measured according to GB/T4608-84
The test method of the molten finger refers to GB/T3682-2000
Table one: experimental data comparison table
Table two: raw material table
The main body of the hot melt adhesive is mainly prepared by reacting diamine with dibasic acid to obtain a polyamide body, then adding excessive dihydric alcohol to carry out end capping to obtain a polymer with two ends being hydroxyl groups, then polymerizing an acyl chloride compound on the hydroxyl group at one end of the polymer under the catalysis of organic weak base and a catalyst, and adding diethylene glycol monovinyl ether, wherein one end of the diethylene glycol monovinyl ether can be polymerized on the hydroxyl group at one end of the polymer, and the other end of the diethylene glycol monovinyl ether is also hydroxyl group, so that the diethylene glycol monovinyl ether can be continuously polymerized, and the ether modified polyamide body is obtained.
Compared with the comparative example, the embodiment obviously shows that the tensile strength and the peel strength of the polyamide hot melt adhesive modified by the technical scheme of the invention are improved, and the melting point is reduced and the melt index is improved due to the introduction of ether bonds.
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 (4)
1. An ether modified reinforced hot melt adhesive is characterized in that:
comprises the following components in parts by mole:
acid chloride-based compound: 1 to 2 portions of
Diamine (b): 20 to 30 portions of
Dibasic acid: 20 to 30 portions of
A dihydric alcohol: 2 to 10 portions of
Diethylene glycol monovinyl ether: 1-5 parts;
the acyl chloride-based compound is at least one of acryloyl chloride, methacryloyl chloride and butenoyl chloride;
the diamine is at least one of ethylenediamine, propylenediamine, butanediamine, pentanediamine, hexanediamine, decanediamine, dodecanediamine, 2, 3-dimethylbutanediamine, 2-methylpentanediamine, 2-hexanediamine and 2, 2, 4-methylhexanediamine;
the dibasic acid is at least one of succinic acid, glutaric acid, adipic acid, 2-methyl adipic acid, 1, 2-dimethyl adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid;
the dihydric alcohol is at least one of ethylene glycol, propylene glycol, butanediol and pentanediol;
the preparation method comprises the following steps:
the method comprises the following steps: adding dibasic acid and diamine into a reaction kettle, heating to 100-130 ℃, and preserving heat for 1 hour;
step two: continuously heating to 200-230 ℃ for continuous reaction for 1 hour, adding excessive diol for end capping, reacting at 200-230 ℃ for 0.5-1 hour, and reacting at 230-270 ℃ with a vacuum degree of 0.09MPa for 1 hour to obtain a polymer;
step three: adding organic weak base and a catalyst into the polymer at room temperature, then adding an acyl chloride compound and diethylene glycol monovinyl ether, and reacting for 10-15 hours at room temperature;
step four: and preserving the temperature to 20-30 ℃, and reacting for 10-20 hours to obtain the hot melt adhesive.
2. The ether modified reinforced hot melt adhesive as claimed in claim 1, wherein:
the organic weak base is triethylamine;
the catalyst is p-toluenesulfonic acid.
3. The ether modified reinforced hot melt adhesive as claimed in claim 2, wherein:
the dosage of the organic weak base is 1-2 parts by mole;
the amount of the catalyst is 0.05-0.1 part by mole.
4. The ether modified reinforced hot melt adhesive as claimed in claim 1, wherein:
the first step, the second step and the third step are carried out under the protection of nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011643914.1A CN112795362B (en) | 2020-12-31 | 2020-12-31 | Ether modified reinforced hot melt adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011643914.1A CN112795362B (en) | 2020-12-31 | 2020-12-31 | Ether modified reinforced hot melt adhesive |
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| Publication Number | Publication Date |
|---|---|
| CN112795362A CN112795362A (en) | 2021-05-14 |
| CN112795362B true CN112795362B (en) | 2022-06-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011643914.1A Active CN112795362B (en) | 2020-12-31 | 2020-12-31 | Ether modified reinforced hot melt adhesive |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013082919A (en) * | 2011-09-28 | 2013-05-09 | Sekisui Fuller Co Ltd | Moisture-curable hot-melt adhesive |
| CN105504271A (en) * | 2016-02-03 | 2016-04-20 | 温州华特热熔胶有限公司 | Low-melting-point copolyamide hot melt adhesive for clothes and processing method thereof |
| WO2017080494A1 (en) * | 2015-11-13 | 2017-05-18 | 昆山天洋热熔胶有限公司 | High-performance polyamide hot melt adhesive for surface decoration and preparation method therefor |
| CN107556965A (en) * | 2017-09-20 | 2018-01-09 | 华特粘接材料股份有限公司 | High temperature resistant copolyamide PUR and processing method for footwear material |
| CN109880574A (en) * | 2019-03-06 | 2019-06-14 | 温州包鹿新材料有限公司 | Antibacterial flame-retardant modified glass glue and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2974095B1 (en) * | 2011-04-13 | 2014-08-22 | Rhodia Operations | STABILIZED POLYAMIDE |
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2020
- 2020-12-31 CN CN202011643914.1A patent/CN112795362B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013082919A (en) * | 2011-09-28 | 2013-05-09 | Sekisui Fuller Co Ltd | Moisture-curable hot-melt adhesive |
| WO2017080494A1 (en) * | 2015-11-13 | 2017-05-18 | 昆山天洋热熔胶有限公司 | High-performance polyamide hot melt adhesive for surface decoration and preparation method therefor |
| CN105504271A (en) * | 2016-02-03 | 2016-04-20 | 温州华特热熔胶有限公司 | Low-melting-point copolyamide hot melt adhesive for clothes and processing method thereof |
| CN107556965A (en) * | 2017-09-20 | 2018-01-09 | 华特粘接材料股份有限公司 | High temperature resistant copolyamide PUR and processing method for footwear material |
| CN109880574A (en) * | 2019-03-06 | 2019-06-14 | 温州包鹿新材料有限公司 | Antibacterial flame-retardant modified glass glue and preparation method thereof |
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| CN112795362A (en) | 2021-05-14 |
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