CN105542698B - Antibacterial low melting point hot melt adhesive and preparation method thereof - Google Patents
Antibacterial low melting point hot melt adhesive and preparation method thereof Download PDFInfo
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- CN105542698B CN105542698B CN201511013992.2A CN201511013992A CN105542698B CN 105542698 B CN105542698 B CN 105542698B CN 201511013992 A CN201511013992 A CN 201511013992A CN 105542698 B CN105542698 B CN 105542698B
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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
- C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic 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
- C08G63/78—Preparation processes
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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
- 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
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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
- 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
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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
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to a kind of antibacterial low melting point hot melt adhesive, the hot melt adhesive is formed by the Raw material processing of following parts by weight: 40-80 parts of polyester hot-melt adhesive, 20-30 parts of polyamide, 3-8 parts of paraffin, 164 0.5-1 parts of antioxidant, 0.5-1 parts of inorganic antiseptic；The polyester hot-melt adhesive of formula ratio, polyamide, paraffin, antioxidant and inorganic antiseptic are uniformly mixed; it is then added in screw extruder pelletizer; melt blending squeezes out; for the mixed material of extrusion through cooling, granulation, granulation acquisition pellet is vacuum dried to go moisture removal to obtain antibacterial low melting point hot melt adhesive；The present invention selects the polyester hot-melt adhesive of low melting point to mix with polyamide, paraffin, antioxidant, inorganic antiseptic, cohesive force stabilization is made, is not easy the hot melt adhesive gone mouldy, solidification rate is fast, it is easy to use, it is affected by environment small, especially under low temperature environment, solidification rate substantially increases production efficiency also superior to the hot melt adhesive of the prior art, the cooling and solidifying time after hot melt adhesive coating substantially shortens, and coating efficiency significantly improves.
Description
Technical field
The present invention relates to a kind of antibacterial low melting point hot melt adhesive and preparation method thereof.
Background technique
Polyester hot-melt adhesive is a kind of environment-friendly type hot melt glue, high with bonding action, prominent to the Optical instrument of polar material,
The advantages that electrical property and excellent chemical mediator-resitant property, is widely used in weaving, clothes, automobile, packaging, shoemaking, electronics, building materials etc.
Rapid growth momentum is presented in industry in recent years.Polyester hot-melt adhesive is with aromatic acid and aliphatic dibasic acid, aliphatic
Dihydric alcohol is raw material, is obtained through copolycondensation.With the implementation of low-carbon economy, low application temperature becomes hot melt adhesive property development
One of direction, this requires polyester hot-melt adhesives to have lower fusing point.However the crystalline rate of low-melting point polyester hot melt adhesive is slower,
It needs long period drying that could wind after leading to product gluing, otherwise will appear interlayer adhesion, generate waste product, greatly reduce life
Efficiency is produced, in addition, hot melt adhesive in the prior art without bacteria resistance function, has the risk of mildew after use.
Summary of the invention
It is an object of the invention to solve the deficiencies in the prior art, a kind of antibacterial low melting point hot melt adhesive and its preparation side are provided
Method.
The technical solution adopted by the present invention to solve the technical problems is:
Antibacterial low melting point hot melt adhesive, the hot melt adhesive are formed by the Raw material processing of following parts by weight:
It is 40-80 parts of polyester hot-melt adhesive, 20-30 parts of polyamide, 3-8 parts of paraffin, 164 0.5-1 parts of antioxidant, inorganic
0.5-1 parts of antibacterial agent；
The polyester hot-melt adhesive of formula ratio, polyamide, paraffin, antioxidant and inorganic antiseptic are uniformly mixed, then
It is added in screw extruder pelletizer, melt blending squeezes out, and the mixed material of extrusion is granulated through cooling, granulation and obtains pellet warp
Vacuum drying goes moisture removal to obtain antibacterial low melting point hot melt adhesive；
The polyester hot-melt adhesive is prepared as follows:
(1) proper amount of nano grade bentonite is added in reaction kettle and disperses to form uniform and stable slurry with butanediol；
(2) it is added under agitation into the reaction kettle of step (1) by dimethyl terephthalate (DMT), M-phthalic acid two
Methyl esters, dimeric dibasic acid, after mixing, be added four positive definite butyl ester of proper catalyst metatitanic acid, under nitrogen protection in 205-215 DEG C into
Row ester exchange reaction 1-2 hours, then the tetra-n-butyl titanate of hydrogenation of liquid polybutadiene dihydric alcohol and surplus is added, under vacuum
210-230 DEG C of heating carries out polycondensation 3-4 hours, obtains polyester precursor copolymer i.e. polyester hot-melt adhesive；
The dimethyl terephthalate (DMT), 1,4-butanediol, dimethyl isophthalate, tetra-n-butyl titanate, dimerization
The molar ratio of acid, hydrogenation of liquid polybutadiene dihydric alcohol are as follows: (80-85): 200:20:(0.02-0.03): 30:15；
The dimeric dibasic acid is the binary acid containing 36 carbon atoms, and the inorganic antiseptic is zinc oxide or copper oxide.
Preferably, the hot melt adhesive is made of the raw material of following parts by weight: 60 parts of polyester hot-melt adhesive, polyamide 25
Part, 5 parts of paraffin, 164 0.75 parts of antioxidant, 0.75 part of inorganic antiseptic.
Preferably, the dosage molar ratio of four positive definite butyl ester of ester exchange reaction and the catalyst metatitanic acid of polycondensation reaction is 1:2.
Preferably, the nanoscale bentonite selects nanoscale organobentonite.
Preferably, the bentonitic dosage of the nanoscale is 0.5-1.0mol.
The beneficial effects of the present invention are:
It is lower and be capable of the poly- of rapid crystallization that the present invention is prepared for fusing point by the way of nanoscale bentonite in-situ polymerization
Ester hot melt adhesive, polyester hot-melt adhesive fusing point obtained is close with the fusing point of low melting point hot melt adhesive in the prior art, and viscosity performance is more
It is excellent；
The present invention selects the polyester hot-melt adhesive of low melting point to mix with polyamide, paraffin, antioxidant, inorganic antiseptic,
Obtained cohesive force is stable, is not easy the hot melt adhesive gone mouldy, solidification rate is fast, easy to use, affected by environment small, especially low temperature ring
Under border, solidification rate substantially increases production efficiency, the cooling and solidifying after hot melt adhesive coating also superior to the hot melt adhesive of the prior art
Time substantially shortens and coating efficiency significantly improves.
Specific embodiment
Below by specific embodiment, technical scheme of the present invention will be further explained in detail.
Embodiment 1:
Antibacterial low melting point hot melt adhesive, the hot melt adhesive are formed by the Raw material processing of following parts by weight:
40 parts of polyester hot-melt adhesive, 20 parts of polyamide, 3 parts of paraffin, 164 0.5 parts of antioxidant, 0.5 part of zinc oxide；
The polyester hot-melt adhesive of formula ratio, polyamide, paraffin, antioxidant and inorganic antiseptic are uniformly mixed, then
It is added in screw extruder pelletizer, melt blending squeezes out, and the mixed material of extrusion is granulated through cooling, granulation and obtains pellet warp
Vacuum drying goes moisture removal to obtain antibacterial low melting point hot melt adhesive；
The polyester hot-melt adhesive is prepared as follows:
(1) proper amount of nano grade bentonite is added in reaction kettle and disperses to form uniform and stable slurry with butanediol；
(2) it is added under agitation into the reaction kettle of step (1) by dimethyl terephthalate (DMT), M-phthalic acid two
Methyl esters, dimeric dibasic acid, after mixing, be added four positive definite butyl ester of proper catalyst metatitanic acid, under nitrogen protection in 205-215 DEG C into
Row ester exchange reaction 1-2 hours, then the tetra-n-butyl titanate of hydrogenation of liquid polybutadiene dihydric alcohol and surplus is added, under vacuum
210-230 DEG C of heating carries out polycondensation 3-4 hours, obtains polyester precursor copolymer i.e. polyester hot-melt adhesive；
The dimethyl terephthalate (DMT), 1,4-butanediol, dimethyl isophthalate, tetra-n-butyl titanate, dimerization
The molar ratio of acid, hydrogenation of liquid polybutadiene dihydric alcohol are as follows: 80:200:20:0.02:30:15；
The dimeric dibasic acid is the binary acid containing 36 carbon atoms；
The dosage molar ratio of four positive definite butyl ester of ester exchange reaction and the catalyst metatitanic acid of polycondensation reaction is 1:2.
The nanoscale bentonite selects nanoscale organobentonite, and the bentonitic dosage of nanoscale is 0.5mol.
Embodiment 2:
Antibacterial low melting point hot melt adhesive, the hot melt adhesive are formed by the Raw material processing of following parts by weight:
80 parts of polyester hot-melt adhesive, 30 parts of polyamide, 8 parts of paraffin, 164 1.0 parts of antioxidant, 1.0 parts of copper oxide；
The polyester hot-melt adhesive of formula ratio, polyamide, paraffin, antioxidant and inorganic antiseptic are uniformly mixed, then
It is added in screw extruder pelletizer, melt blending squeezes out, and the mixed material of extrusion is granulated through cooling, granulation and obtains pellet warp
Vacuum drying goes moisture removal to obtain antibacterial low melting point hot melt adhesive；
The polyester hot-melt adhesive is prepared as follows:
(1) proper amount of nano grade bentonite is added in reaction kettle and disperses to form uniform and stable slurry with butanediol；
(2) it is added under agitation into the reaction kettle of step (1) by dimethyl terephthalate (DMT), M-phthalic acid two
Methyl esters, dimeric dibasic acid, after mixing, be added four positive definite butyl ester of proper catalyst metatitanic acid, under nitrogen protection in 205-215 DEG C into
Row ester exchange reaction 1-2 hours, then the tetra-n-butyl titanate of hydrogenation of liquid polybutadiene dihydric alcohol and surplus is added, under vacuum
210-230 DEG C of heating carries out polycondensation 3-4 hours, obtains polyester precursor copolymer i.e. polyester hot-melt adhesive；
The dimethyl terephthalate (DMT), 1,4-butanediol, dimethyl isophthalate, tetra-n-butyl titanate, dimerization
The molar ratio of acid, hydrogenation of liquid polybutadiene dihydric alcohol are as follows: 85:200:20:0.03:30:15；
The dimeric dibasic acid is the binary acid containing 36 carbon atoms；
The dosage molar ratio of four positive definite butyl ester of ester exchange reaction and the catalyst metatitanic acid of polycondensation reaction is 1:2.
The nanoscale bentonite selects nanoscale organobentonite, and the bentonitic dosage of nanoscale is 1mol.
Embodiment 3:
Antibacterial low melting point hot melt adhesive, the hot melt adhesive are formed by the Raw material processing of following parts by weight:
60 parts of polyester hot-melt adhesive, 25 parts of polyamide, 5 parts of paraffin, 164 0.75 parts of antioxidant, 0.75 part of copper oxide；
The polyester hot-melt adhesive of formula ratio, polyamide, paraffin, antioxidant and inorganic antiseptic are uniformly mixed, then
It is added in screw extruder pelletizer, melt blending squeezes out, and the mixed material of extrusion is granulated through cooling, granulation and obtains pellet warp
Vacuum drying goes moisture removal to obtain antibacterial low melting point hot melt adhesive；
The polyester hot-melt adhesive is prepared as follows:
(1) proper amount of nano grade bentonite is added in reaction kettle and disperses to form uniform and stable slurry with butanediol；
(2) it is added under agitation into the reaction kettle of step (1) by dimethyl terephthalate (DMT), M-phthalic acid two
Methyl esters, dimeric dibasic acid, after mixing, be added four positive definite butyl ester of proper catalyst metatitanic acid, under nitrogen protection in 205-215 DEG C into
Row ester exchange reaction 1-2 hours, then the tetra-n-butyl titanate of hydrogenation of liquid polybutadiene dihydric alcohol and surplus is added, under vacuum
210-230 DEG C of heating carries out polycondensation 3-4 hours, and obtained polyester precursor copolymer is hot pressed into film in 170-180 DEG C；
The dimethyl terephthalate (DMT), 1,4-butanediol, dimethyl isophthalate, tetra-n-butyl titanate, dimerization
The molar ratio of acid, hydrogenation of liquid polybutadiene dihydric alcohol are as follows: 82:200:20:0.24:30:15；
The dimeric dibasic acid is the binary acid containing 36 carbon atoms；
The dosage molar ratio of four positive definite butyl ester of ester exchange reaction and the catalyst metatitanic acid of polycondensation reaction is 1:2.
The nanoscale bentonite selects nanoscale organobentonite, and the bentonitic dosage of nanoscale is 0.75mol.
It is lower and be capable of the poly- of rapid crystallization that the present invention is prepared for fusing point by the way of nanoscale bentonite in-situ polymerization
Ester hot melt adhesive, polyester hot-melt adhesive fusing point obtained is close with the fusing point of low melting point hot melt adhesive in the prior art, and viscosity performance is more
It is excellent；
The present invention selects the polyester hot-melt adhesive of low melting point to mix with polyamide, paraffin, antioxidant, inorganic antiseptic,
Obtained cohesive force is stable, is not easy the hot melt adhesive gone mouldy, solidification rate is fast, easy to use, affected by environment small, especially low temperature ring
Under border, solidification rate substantially increases production efficiency, the cooling and solidifying after hot melt adhesive coating also superior to the hot melt adhesive of the prior art
Time substantially shortens and coating efficiency significantly improves.
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form
Limitation, there are also other variations and modifications on the premise of not exceeding the technical scheme recorded in the claims.
Claims (3)
1. antibacterial low melting point hot melt adhesive, it is characterised in that: the hot melt adhesive is formed by the Raw material processing of following parts by weight:
40-80 parts of polyester hot-melt adhesive, 20-30 parts of polyamide, 3-8 parts of paraffin, 164 0.5-1 parts of antioxidant, inorganic antibacterial
0.5-1 parts of agent；
The polyester hot-melt adhesive of formula ratio, polyamide, paraffin, antioxidant and inorganic antiseptic are uniformly mixed, are then added
Into screw extruder pelletizer, melt blending is squeezed out, and the mixed material of extrusion is granulated through cooling, granulation and obtains pellet through vacuum
It is dry that moisture removal is gone to obtain antibacterial low melting point hot melt adhesive；
The polyester hot-melt adhesive is prepared as follows:
(1) proper amount of nano grade bentonite is added in reaction kettle and disperses to form uniform and stable slurry with butanediol；
(2) under agitation into the reaction kettle of step (1) be added dimethyl terephthalate (DMT), dimethyl isophthalate,
After mixing proper catalyst tetra-n-butyl titanate is added, under nitrogen protection in 205-215 DEG C of progress ester friendship in dimeric dibasic acid
Reaction 1-2 hours is changed, then adds the tetra-n-butyl titanate of hydrogenation of liquid polybutadiene dihydric alcohol and surplus, the 210- under vacuum
230 DEG C of heating carry out polycondensation 3-4 hours, obtain polyester precursor copolymer i.e. polyester hot-melt adhesive；
The dimethyl terephthalate (DMT), butanediol, dimethyl isophthalate, tetra-n-butyl titanate, dimeric dibasic acid, hydrogenation of liquid
The molar ratio of polybutadiene dihydric alcohol are as follows: (80-85): 200:20:(0.02-0.03): 30:15；
The dimeric dibasic acid is the binary acid containing 36 carbon atoms, and the inorganic antiseptic is zinc oxide or copper oxide；
The nanoscale bentonite selects nanoscale organobentonite, and the bentonitic dosage of nanoscale is 0.5-1.0mol.
2. antibacterial low melting point hot melt adhesive according to claim 1, it is characterised in that: the hot melt adhesive is by following parts by weight
Raw material composition: 60 parts of polyester hot-melt adhesive, 25 parts of polyamide, 5 parts of paraffin, 164 0.75 parts of antioxidant, inorganic antiseptic
0.75 part.
3. antibacterial low melting point hot melt adhesive according to claim 1 or 2, it is characterised in that: ester exchange reaction and polycondensation reaction
Catalyst tetra-n-butyl titanate dosage molar ratio be 1:2.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201511013992.2A CN105542698B (en) | 2015-12-31 | 2015-12-31 | Antibacterial low melting point hot melt adhesive and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511013992.2A CN105542698B (en) | 2015-12-31 | 2015-12-31 | Antibacterial low melting point hot melt adhesive and preparation method thereof |
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| CN105542698A CN105542698A (en) | 2016-05-04 |
| CN105542698B true CN105542698B (en) | 2018-12-18 |
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| CN108559433B (en) * | 2018-05-14 | 2021-02-26 | 启东鑫天鼎热熔胶有限公司 | Formula and preparation method of high-temperature-resistant polyester hot melt adhesive |
| CN108913079B (en) * | 2018-05-14 | 2020-12-22 | 启东鑫天鼎热熔胶有限公司 | Formula and preparation method of low-temperature-resistant polyester hot melt adhesive |
| CN113930891A (en) * | 2021-10-22 | 2022-01-14 | 海宁市立达经编布业有限公司 | Zinc antibacterial elastic breathable fabric and production process thereof |
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| CN102675609B (en) * | 2012-06-07 | 2013-09-18 | 昆山天洋热熔胶有限公司 | Rapid crystallization type nanometer composite polyester hot melt adhesive and preparing process thereof |
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Effective date of registration: 20191220 Address after: No.1, East SANHENG Road, Hejiao Industrial Avenue, Hejiao village, Nanzhuang Town, Chancheng District, Foshan City, Guangdong Province 528000 Patentee after: Foshan GAODA resin Co., Ltd Address before: Anyang Street Hill Road East of Ruian city Wenzhou 325000 Zhejiang Province, Lane 295, No. 6 6-7 4 Patentee before: Lin Chuhuang |