CN108641664B - Formula and preparation method of easy-to-rebound polyamide hot melt adhesive - Google Patents
Formula and preparation method of easy-to-rebound polyamide hot melt adhesive Download PDFInfo
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 63
- 239000004952 Polyamide Substances 0.000 title claims abstract description 54
- 229920002647 polyamide Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims description 14
- 238000009472 formulation Methods 0.000 title description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 43
- 229920000570 polyether Polymers 0.000 claims abstract description 43
- 150000002148 esters Chemical class 0.000 claims abstract description 40
- 239000000835 fiber Substances 0.000 claims abstract description 34
- 239000000945 filler Substances 0.000 claims abstract description 25
- 239000007822 coupling agent Substances 0.000 claims abstract description 21
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 20
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 20
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 12
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 12
- 229920001400 block copolymer Polymers 0.000 claims abstract description 12
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 12
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 58
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 58
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 29
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 23
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 22
- -1 polybutylene terephthalate Polymers 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000539 dimer Substances 0.000 claims description 17
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 14
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 14
- 229960004488 linolenic acid Drugs 0.000 claims description 14
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 14
- 238000006068 polycondensation reaction Methods 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 11
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 11
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 10
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000012644 addition polymerization Methods 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 239000004200 microcrystalline wax Substances 0.000 claims description 9
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229920001748 polybutylene Polymers 0.000 claims description 9
- 238000005070 sampling Methods 0.000 claims description 9
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 150000004985 diamines Chemical class 0.000 claims description 5
- 239000012188 paraffin wax Substances 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 abstract description 6
- 239000000806 elastomer Substances 0.000 abstract description 6
- 239000004744 fabric Substances 0.000 abstract description 5
- 238000002844 melting Methods 0.000 abstract description 5
- 230000008018 melting Effects 0.000 abstract description 5
- 229920000728 polyester Polymers 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- 230000009477 glass transition Effects 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 15
- 235000020778 linoleic acid Nutrition 0.000 description 15
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 15
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010923 batch production Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polyamides (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a formula of an easily rebounded polyamide hot melt adhesive, which comprises the following components in parts by mass: 35-46 parts of polyamide resin; 10-15 parts of polyether ester fiber; 18-25 parts of a filler; 8-12 parts of rosin resin; 2-3 parts of a coupling agent; 1-2 parts of an antioxidant. The polyether ester fiber is spun by a polyether ester elastomer, the polyether ester elastomer is a block copolymer formed by copolymerizing a polyester chain segment with high crystallinity and high melting point as a hard segment and amorphous polyether with lower glass transition temperature as a soft segment, a hard segment region provides thermally reversible physical crosslinking for a soft segment region, good thermoplasticity is endowed, the soft segment and the soft segment are connected by chemical bonds, and the polyether ester fiber has good elastic recovery rate and elastic stability. The polyether ester fiber is blended into the polyamide hot melt adhesive to modify the polyamide hot melt adhesive, so that the polyamide hot melt adhesive has better resilience, and the lining cloth and the like bonded by the modified polyamide hot melt adhesive can be quickly restored to deform after being pressed and bent, thereby keeping the shapes of clothes, shoes and caps.
Description
Technical Field
The invention relates to the field of hot melt adhesives, in particular to a formula of an easily rebounded polyamide hot melt adhesive and a preparation method thereof.
Background
The preparation method of the polyamide hot melt adhesive comprises the steps of directly carrying out copolymerization polymerization on dibasic acid and diamine, and then carrying out modification and crushing to obtain the polyamide hot melt adhesive. The production process of the polyamide hot melt adhesive is simple, the equipment requirement is low, the raw materials are easy to obtain, the cost is low, the operation and the control are convenient and accurate, the stable product quality is ensured, the product bonding performance is excellent, the large-scale production and the small-batch production can be realized, and the polyamide hot melt adhesive is flexible and convenient and is easy to popularize and apply.
The polyamide hot melt adhesive is widely used for producing clothes, shoes and hats, wherein part of clothes, shoes and hats need to have stiff and plump appearance, and the polyamide hot melt adhesive used as the hot melt adhesive for bonding the lining cloth needs to have better rebound resilience, so that the polyamide hot melt adhesive can still help the clothes, shoes, hats and the like to recover the shape after being impacted by extrusion and the like.
Disclosure of Invention
The invention aims to provide a formula of an easily rebounded polyamide hot melt adhesive and a preparation method thereof, and the easily rebounded polyamide hot melt adhesive has the advantage of good rebound force.
The technical purpose of the invention is realized by the following technical scheme: the formula of the easy-resilience polyamide hot melt adhesive comprises the following components in parts by mass:
by adopting the technical scheme, the polyether ester fiber is spun by the polyether ester elastomer, the polyether ester elastomer takes a polyester chain segment with high crystallinity and high melting point as a hard segment, amorphous polyether with lower glass transition temperature as a block copolymer formed by copolymerization of a soft segment, the hard segment region provides thermally reversible physical crosslinking for the soft segment region, good thermoplasticity is endowed, the soft segment and the soft segment are connected by chemical bonds, and the polyether ester fiber has better elastic recovery rate and elastic stability. The polyether ester fiber is blended into the polyamide hot melt adhesive to modify the polyamide hot melt adhesive, so that the polyamide hot melt adhesive has better resilience, and the lining cloth and the like bonded by the modified polyamide hot melt adhesive can be quickly restored to deform after being pressed and bent, thereby keeping the shapes of clothes, shoes and caps. The filler mainly reduces the cost, reduces the contractibility of the hot melt adhesive during solidification, changes the crystallization speed, prevents adhesive penetration and improves the heat resistance of the hot melt adhesive. The coupling agent strengthens the combination of the polyamide resin and the polyether ester fiber, simultaneously can improve the dispersibility and the adhesive force of the filler in the resin, strengthens the wetting capacity of the hot melt adhesive to the bonding surface, and improves the bonding strength, the water resistance, the weather resistance and other properties. When the melt viscosity of the hot melt adhesive polymer is high, the rosin resin can increase the wettability and the bonding force of the hot melt adhesive to a base material, and reduce the melt viscosity of the polymer, so that the bonding strength is improved.
Further, the polyether ester fiber is a block copolymer composed of high-crystallinity hard segment polybutylene terephthalate (PBT) and soft segment polybutylene glycol ether, and the mass fraction of the hard segment chain is 40%.
By adopting the technical scheme, the polyether ester fiber composed of the high-crystallinity hard-chain segment polybutylene terephthalate (PBT) and the soft-chain segment polybutylene terephthalate has better rebound resilience, and when the mass fraction of the high-crystallinity hard-chain segment polybutylene terephthalate (PBT) accounts for 40%, the rebound resilience and the elongation at break of the polyether ester fiber are better, so that the blending modified polyamide hot melt adhesive has better elastic deformation recovery capability.
Further, the polyamide resin is a polycondensation polymer of dibasic acid and diamine, the dibasic acid comprises dimer linolenic acid and sebacic acid, and the diamine comprises ethylenediamine and hexamethylenediamine.
By adopting the technical scheme, the polyamide resin is a matrix resin of the polyamide hot melt adhesive, and a polycondensation type high molecular compound with a-CONH structure in the molecule. The polyamide prepared by polycondensation of the raw materials of dimer linolenic acid, sebacic acid, ethylenediamine and hexamethylenediamine has a higher melting point.
Further, the mole ratio of the dimeric linolenic acid to the sebacic acid is 1: 0.5.
by adopting the technical scheme, the dimerized linoleic acid and the sebacic acid in the proportion meet the reaction requirement.
Further, the molar ratio of the ethylene diamine to the hexamethylene diamine is 1: 1.2.
by adopting the technical scheme, the ethylenediamine and the hexamethylenediamine in the proportion meet the reaction requirement.
Furthermore, the coupling agent is glycidoxypropyltrimethoxysilane or vinyltrimethoxysilane.
By adopting the technical scheme, the glycidoxypropyltrimethoxysilane enhances the combination of the polyamide resin and the polyether ester fiber, improves the dispersibility and the adhesive force of the filler in the resin and ensures that the hot melt adhesive can be tightly combined with various bonding surfaces.
Further, the paint also comprises 10-15 parts of microcrystalline paraffin.
By adopting the technical scheme, the microcrystalline wax is a refined synthetic wax with approximate microcrystalline property, has the characteristics of good gloss, high melting point and light color, and has a compact, firm and smooth structure.
Further, the antioxidant is 2, 6-di-tert-butyl-p-cresol.
By adopting the technical scheme, the 2, 6-di-tert-butyl-p-cresol can inhibit or delay the thermal oxidation of high polymers and other organic compounds in the air.
Further, the filler is nano calcium carbonate.
By adopting the technical scheme, the nano calcium carbonate has good thermal stability, and the polyester hot melt adhesive taking the nano calcium carbonate as the filler has reduced thermal expansion coefficient and shrinkage rate and higher thermal stability.
The preparation method of the easy-resilience polyamide hot melt adhesive is characterized by comprising the following steps of:
s1, stirring dimerized linolenic acid and sebacic acid under the protection of nitrogen, starting to dropwise add a mixture of ethylenediamine and hexamethylenediamine when slowly heating to 125-140 ℃, controlling the temperature to 140-155 ℃, heating to 205-220 ℃ after dropwise adding, continuing to react under the condition of 1.5-1.8 Mpa, and finishing polycondensation when the water content of a product is close to 95% of a theoretical value;
s2, adding an antioxidant into the product of S1, reducing pressure, performing addition polymerization under the conditions of 1.6-2.7 kPa and 220-230 ℃, and sampling to determine an amine value after 1h of reaction, wherein the amine value meets the index;
s3, continuously adding a mixture of polyether ester fibers, fillers, rosin resins, microcrystalline wax and a coupling agent into the product of S2, stirring for 1.5 hours at 255-265 ℃, and modifying the copolymer to obtain a modified finished product of the polyamide hot melt adhesive.
By adopting the technical scheme, the polyamide resin is obtained through polycondensation and polyaddition, and the modified polyamide hot melt adhesive is obtained through copolymer modification.
In conclusion, the invention has the following beneficial effects:
1. the polyamide hot melt adhesive is modified by adding polyether ester fiber, the polyether ester fiber is spun by polyether ester elastomer, the polyether ester elastomer takes a polyester chain segment with high crystallinity and high melting point as a hard segment, amorphous polyether with lower glass transition temperature as a block copolymer formed by copolymerization of a soft segment, the hard segment region provides thermally reversible physical crosslinking for a soft segment region, good thermoplasticity is endowed, the soft segment and the soft segment are connected by chemical bonds, and the polyamide hot melt adhesive has good elastic recovery rate and elastic stability. Polyether ester fibers are blended into the polyamide hot melt adhesive to modify the polyamide hot melt adhesive, so that the polyamide hot melt adhesive has better resilience, and the lining cloth and the like bonded by the modified polyamide hot melt adhesive can be quickly deformed after being pressed and bent, so that the shapes of clothes, shoes and caps are kept;
2. the glycidoxypropyltrimethoxysilane is added when the copolymer is mixed to modify the polyamide resin, so that the combination of the polyamide resin and the polyether ester fiber is enhanced, the dispersity and the adhesive force of the filler in the resin are improved, and the hot melt adhesive can be tightly combined with various bonding surfaces.
Detailed Description
Example 1:
wherein the polyether ester fiber is a block copolymer consisting of high-crystallinity hard segment polybutylene terephthalate (PBT) and soft segment polybutylene glycol ether, and the mass fraction of the hard segment chain is 40%; the polyamide resin is a polymer of dimer linoleic acid and sebacic acid and ethylene diamine and hexamethylene diamine, wherein the mole ratio of the dimer linoleic acid to the sebacic acid is 1: 0.5, the molar ratio of the ethylenediamine to the hexamethylenediamine is 1: 1.2; the filler is selected from nano calcium carbonate; 2, 6-di-tert-butyl-p-cresol is selected as the antioxidant; the coupling agent is glycidoxypropyltrimethoxysilane.
The preparation method comprises the following steps:
s1, stirring dimerized linolenic acid and sebacic acid under the protection of nitrogen, starting to dropwise add a mixture of ethylenediamine and hexamethylenediamine when slowly heating to 125-140 ℃, controlling the temperature to 140-155 ℃, heating to 205-220 ℃ after dropwise adding, continuing to react under the condition of 1.5-1.8 Mpa, and finishing polycondensation when the water content of a product is close to 95% of a theoretical value;
s2, adding 1 part of antioxidant into the product of S1, reducing pressure, performing addition polymerization under the conditions of 1.6-2.7 kPa and 220-230 ℃, sampling after 1h of reaction, and determining an amine value, wherein the amine value meets the index (10 in the embodiment);
s3, continuously adding a mixture of 10 parts of polyether ester fiber, 18 parts of filler, 8 parts of rosin resin, 10 parts of microcrystalline wax and 2 parts of coupling agent into the product of S2, stirring for 1.5 hours at 255-265 ℃, and modifying the copolymer to obtain a modified finished product, namely the polyamide hot melt adhesive.
Example 2:
wherein the polyether ester fiber is a block copolymer consisting of high-crystallinity hard segment polybutylene terephthalate (PBT) and soft segment polybutylene glycol ether, and the mass fraction of the hard segment chain is 40%; the polyamide resin is a polymer of dimer linoleic acid and sebacic acid and ethylene diamine and hexamethylene diamine, wherein the mole ratio of the dimer linoleic acid to the sebacic acid is 1: 0.5, the molar ratio of the ethylenediamine to the hexamethylenediamine is 1: 1.2; the filler is selected from nano calcium carbonate; 2, 6-di-tert-butyl-p-cresol is selected as the antioxidant; the coupling agent is glycidoxypropyltrimethoxysilane.
The preparation method comprises the following steps:
s1, stirring dimerized linolenic acid and sebacic acid under the protection of nitrogen, starting to dropwise add a mixture of ethylenediamine and hexamethylenediamine when slowly heating to 125-140 ℃, controlling the temperature to 140-155 ℃, heating to 205-220 ℃ after dropwise adding, continuing to react under the condition of 1.5-1.8 Mpa, and finishing polycondensation when the water content of a product is close to 95% of a theoretical value;
s2, adding 1 part of antioxidant into the product of S1, reducing pressure, performing addition polymerization under the conditions of 1.6-2.7 kPa and 220-230 ℃, sampling after 1h of reaction, and determining an amine value, wherein the amine value meets the index (10 in the embodiment);
s3, continuously adding a mixture of 11 parts of polyether ester fiber, 18 parts of filler, 8 parts of rosin resin, 10 parts of microcrystalline wax and 2 parts of coupling agent into the product of S2, stirring for 1.5 hours at 255-265 ℃, and modifying the copolymer to obtain a modified finished product, namely the polyamide hot melt adhesive.
Example 3:
wherein the polyether ester fiber is a block copolymer consisting of high-crystallinity hard segment polybutylene terephthalate (PBT) and soft segment polybutylene glycol ether, and the mass fraction of the hard segment chain is 40%; the polyamide resin is a polymer of dimer linoleic acid and sebacic acid and ethylene diamine and hexamethylene diamine, wherein the mole ratio of the dimer linoleic acid to the sebacic acid is 1: 0.5, the molar ratio of the ethylenediamine to the hexamethylenediamine is 1: 1.2; the filler is selected from nano calcium carbonate; 2, 6-di-tert-butyl-p-cresol is selected as the antioxidant; the coupling agent is glycidoxypropyltrimethoxysilane.
The preparation method comprises the following steps:
s1, stirring dimerized linolenic acid and sebacic acid under the protection of nitrogen, starting to dropwise add a mixture of ethylenediamine and hexamethylenediamine when slowly heating to 125-140 ℃, controlling the temperature to 140-155 ℃, heating to 205-220 ℃ after dropwise adding, continuing to react under the condition of 1.5-1.8 Mpa, and finishing polycondensation when the water content of a product is close to 95% of a theoretical value;
s2, adding 1 part of antioxidant into the product of S1, reducing pressure, performing addition polymerization under the conditions of 1.6-2.7 kPa and 220-230 ℃, sampling after 1h of reaction, and determining an amine value, wherein the amine value meets the index (10 in the embodiment);
s3, continuously adding a mixture of 12 parts of polyether ester fiber, 18 parts of filler, 8 parts of rosin resin, 10 parts of microcrystalline wax and 2 parts of coupling agent into the product of S2, stirring for 1.5 hours at 255-265 ℃, and modifying the copolymer to obtain a modified finished product, namely the polyamide hot melt adhesive.
Example 4:
wherein the polyether ester fiber is a block copolymer consisting of high-crystallinity hard segment polybutylene terephthalate (PBT) and soft segment polybutylene glycol ether, and the mass fraction of the hard segment chain is 40%; the polyamide resin is a polymer of dimer linoleic acid and sebacic acid and ethylene diamine and hexamethylene diamine, wherein the mole ratio of the dimer linoleic acid to the sebacic acid is 1: 0.5, the molar ratio of the ethylenediamine to the hexamethylenediamine is 1: 1.2; the filler is selected from nano calcium carbonate; 2, 6-di-tert-butyl-p-cresol is selected as the antioxidant; the coupling agent is glycidoxypropyltrimethoxysilane.
The preparation method comprises the following steps:
s1, stirring dimerized linolenic acid and sebacic acid under the protection of nitrogen, starting to dropwise add a mixture of ethylenediamine and hexamethylenediamine when slowly heating to 125-140 ℃, controlling the temperature to 140-155 ℃, heating to 205-220 ℃ after dropwise adding, continuing to react under the condition of 1.5-1.8 Mpa, and finishing polycondensation when the water content of a product is close to 95% of a theoretical value;
s2, adding 2 parts of antioxidant into the product of S1, reducing pressure, performing addition polymerization under the conditions of 1.6-2.7 kPa and 220-230 ℃, sampling after 1 hour of reaction, and determining an amine value, wherein the amine value meets the index (10 in the embodiment);
s3, continuously adding a mixture of 13 parts of polyether ester fiber, 25 parts of filler, 12 parts of rosin resin, 15 parts of microcrystalline wax and 3 parts of coupling agent into the product of S2, stirring for 1.5 hours at the temperature of 255-265 ℃, and modifying the copolymer to obtain a modified finished product polyamide hot melt adhesive.
Example 5:
wherein the polyether ester fiber is a block copolymer consisting of high-crystallinity hard segment polybutylene terephthalate (PBT) and soft segment polybutylene glycol ether, and the mass fraction of the hard segment chain is 40%; the polyamide resin is a polymer of dimer linoleic acid and sebacic acid and ethylene diamine and hexamethylene diamine, wherein the mole ratio of the dimer linoleic acid to the sebacic acid is 1: 0.5, the molar ratio of the ethylenediamine to the hexamethylenediamine is 1: 1.2; the filler is selected from nano calcium carbonate; 2, 6-di-tert-butyl-p-cresol is selected as the antioxidant; the coupling agent is glycidoxypropyltrimethoxysilane.
The preparation method comprises the following steps:
s1, stirring dimerized linolenic acid and sebacic acid under the protection of nitrogen, starting to dropwise add a mixture of ethylenediamine and hexamethylenediamine when slowly heating to 125-140 ℃, controlling the temperature to 140-155 ℃, heating to 205-220 ℃ after dropwise adding, continuing to react under the condition of 1.5-1.8 Mpa, and finishing polycondensation when the water content of a product is close to 95% of a theoretical value;
s2, adding 2 parts of antioxidant into the product of S1, reducing pressure, performing addition polymerization under the conditions of 1.6-2.7 kPa and 220-230 ℃, sampling after 1 hour of reaction, and determining an amine value, wherein the amine value meets the index (10 in the embodiment);
s3, continuously adding a mixture of 14 parts of polyether ester fiber, 25 parts of filler, 12 parts of rosin resin, 15 parts of microcrystalline paraffin and 3 parts of coupling agent into the product of S2, stirring for 1.5 hours at 255-265 ℃, and modifying the copolymer to obtain a modified finished product, namely the polyamide hot melt adhesive.
Example 6:
wherein the polyether ester fiber is a block copolymer consisting of high-crystallinity hard segment polybutylene terephthalate (PBT) and soft segment polybutylene glycol ether, and the mass fraction of the hard segment chain is 40%; the polyamide resin is a polymer of dimer linoleic acid and sebacic acid and ethylene diamine and hexamethylene diamine, wherein the mole ratio of the dimer linoleic acid to the sebacic acid is 1: 0.5, the molar ratio of the ethylenediamine to the hexamethylenediamine is 1: 1.2; the filler is selected from nano calcium carbonate; 2, 6-di-tert-butyl-p-cresol is selected as the antioxidant; the coupling agent is glycidoxypropyltrimethoxysilane.
The preparation method comprises the following steps:
s1, stirring dimerized linolenic acid and sebacic acid under the protection of nitrogen, starting to dropwise add a mixture of ethylenediamine and hexamethylenediamine when slowly heating to 125-140 ℃, controlling the temperature to 140-155 ℃, heating to 205-220 ℃ after dropwise adding, continuing to react under the condition of 1.5-1.8 Mpa, and finishing polycondensation when the water content of a product is close to 95% of a theoretical value;
s2, adding 2 parts of antioxidant into the product of S1, reducing pressure, performing addition polymerization under the conditions of 1.6-2.7 kPa and 220-230 ℃, sampling after 1 hour of reaction, and determining an amine value, wherein the amine value meets the index (10 in the embodiment);
s3, continuously adding a mixture of 15 parts of polyether ester fiber, 25 parts of filler, 12 parts of rosin resin, 15 parts of microcrystalline wax and 3 parts of coupling agent into the product of S2, stirring for 1.5 hours at 255-265 ℃, and modifying the copolymer to obtain a modified finished product, namely the polyamide hot melt adhesive.
Example 7 (blank experiment):
wherein the polyether ester fiber is a block copolymer consisting of high-crystallinity hard segment polybutylene terephthalate (PBT) and soft segment polybutylene glycol ether, and the mass fraction of the hard segment chain is 40%; the polyamide resin is a polymer of dimer linoleic acid and sebacic acid and ethylene diamine and hexamethylene diamine, wherein the mole ratio of the dimer linoleic acid to the sebacic acid is 1: 0.5, the molar ratio of the ethylenediamine to the hexamethylenediamine is 1: 1.2; the filler is selected from nano calcium carbonate; 2, 6-di-tert-butyl-p-cresol is selected as the antioxidant; the coupling agent is glycidoxypropyltrimethoxysilane.
The preparation method comprises the following steps:
s1, stirring dimerized linolenic acid and sebacic acid under the protection of nitrogen, starting to dropwise add a mixture of ethylenediamine and hexamethylenediamine when slowly heating to 125-140 ℃, controlling the temperature to 140-155 ℃, heating to 205-220 ℃ after dropwise adding, continuing to react under the condition of 1.5-1.8 Mpa, and finishing polycondensation when the water content of a product is close to 95% of a theoretical value;
s2, adding 2 parts of antioxidant into the product of S1, reducing pressure, performing addition polymerization under the conditions of 1.6-2.7 kPa and 220-230 ℃, sampling after 1 hour of reaction, and determining an amine value, wherein the amine value meets the index (10 in the embodiment);
s3, continuously adding a mixture of 25 parts of filler, 12 parts of rosin resin, 15 parts of microcrystalline wax and 3 parts of coupling agent into the product of S2, stirring for 1.5 hours at the temperature of 255-265 ℃, and modifying the copolymer to obtain a modified finished product of the polyamide hot melt adhesive.
And (3) performance detection: the products of examples 1-7 were tested.
The detection method comprises the following steps: the products of examples 1 to 7 were bonded to leather and a backing cloth, respectively, and after bending, the rebound resilience was measured at 10s, 1min and 5min, respectively.
The detection results are as follows:
| serial number | 10s | 1min | 5min |
| Example 1 | 68％ | 77％ | 82％ |
| Example 2 | 70％ | 82％ | 84％ |
| Example 3 | 74％ | 85％ | 88％ |
| Example 4 | 79％ | 88％ | 95％ |
| Example 5 | 76％ | 83％ | 91％ |
| Example 6 | 73％ | 80％ | 87％ |
| Example 7 (empty) | 55％ | 59％ | 61％ |
Analysis of examples 1-6 and comparison with example 7 shows that the polyamide hot melt adhesive modified by blending with polyether ester fibers according to the formula of the present invention has good resilience, high resilience rate of more than 68% in 10s, fast resilience speed, good resilience performance after 1min and 5min, and resilience rates of more than 77% and 82% respectively; with example 4 being the most effective. The polyamide hot melt adhesive has the advantage of being beneficial to recovering the form of an adhesive.
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. An easy-to-rebound polyamide hot melt adhesive is characterized in that: the adhesive comprises the following components in parts by mass:
35-46 parts of polyamide resin
10-15 parts of polyether ester fiber
18-25 parts of filler
8-12 parts of rosin resin
2-4 parts of coupling agent
1-2 parts of an antioxidant.
2. The easy-to-rebound polyamide hot melt adhesive according to claim 1, which is characterized in that: the polyether ester fiber is a block copolymer consisting of high-crystallinity hard segment polybutylene terephthalate (PBT) and soft segment polybutylene glycol ether, and the mass fraction of the hard segment chain is 40%.
3. The easy-to-rebound polyamide hot melt adhesive according to claim 2, characterized in that: the polyamide resin is a polycondensation polymer of dibasic acid and diamine, the dibasic acid comprises dimer linolenic acid and sebacic acid, and the diamine comprises ethylenediamine and hexamethylenediamine.
4. The easy-to-rebound polyamide hot melt adhesive according to claim 3, wherein: the mol ratio of the dimeric linolenic acid to the sebacic acid is 1: 0.5.
5. the easy-to-rebound polyamide hot melt adhesive according to claim 4, wherein: the molar ratio of the ethylene diamine to the hexamethylene diamine is 1: 1.2.
6. the easy-to-rebound polyamide hot melt adhesive according to claim 5, wherein: the coupling agent is glycidoxypropyltrimethoxysilane or vinyltrimethoxysilane.
7. The easy-to-rebound polyamide hot melt adhesive according to claim 6, which is characterized in that: also comprises 10-15 parts of microcrystalline paraffin.
8. The easy-to-rebound polyamide hot melt adhesive according to claim 7, wherein: the antioxidant is 2, 6-di-tert-butyl-p-cresol.
9. The easy-to-rebound polyamide hot melt adhesive according to claim 8, wherein: the filler is nano calcium carbonate.
10. The preparation method of the easy-resilience polyamide hot melt adhesive is characterized by comprising the following steps of:
s1, stirring dimerized linolenic acid and sebacic acid under the protection of nitrogen, starting to dropwise add a mixture of ethylenediamine and hexamethylenediamine when slowly heating to 125-140 ℃, controlling the temperature to 140-155 ℃, heating to 205-220 ℃ after dropwise adding, continuing to react under the condition of 1.5-1.8 Mpa, and finishing polycondensation when the water content of a product is close to 95% of a theoretical value;
s2, adding an antioxidant into the product of S1, reducing pressure, performing addition polymerization under the conditions of 1.6-2.7 kPa and 220-230 ℃, and sampling to determine an amine value after 1h of reaction, wherein the amine value meets the index;
s3, continuously adding a mixture of polyether ester fibers, fillers, rosin resins, microcrystalline wax and a coupling agent into the product of S2, stirring for 1.5 hours at 255-265 ℃, and modifying the copolymer to obtain a modified finished product of the polyamide hot melt adhesive.
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| EP1389633A1 (en) * | 2002-08-14 | 2004-02-18 | The Procter & Gamble Company | Improved thermoplastic hydrophilic adhesive compositions for dry and wet surfaces the compositions having an increased water adhesion stability |
| EP1749451A1 (en) * | 2005-08-05 | 2007-02-07 | Arkema France | Method for bonding textiles by means of a thermofusible adhesive |
| CN101747499A (en) * | 2008-12-08 | 2010-06-23 | 中国石油天然气股份有限公司 | Thermoplastic block copolyether ester elastomer and preparation method thereof |
| CN102924712A (en) * | 2012-10-18 | 2013-02-13 | 上海天洋热熔胶有限公司 | Low-melting-point polyamide hot melt adhesive with high weather resistance and preparation method thereof |
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