CN108865036A - A kind of modified poly ester hot melt adhesive and preparation method thereof - Google Patents
A kind of modified poly ester hot melt adhesive and preparation method thereof Download PDFInfo
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- CN108865036A CN108865036A CN201810458469.8A CN201810458469A CN108865036A CN 108865036 A CN108865036 A CN 108865036A CN 201810458469 A CN201810458469 A CN 201810458469A CN 108865036 A CN108865036 A CN 108865036A
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- apao
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 109
- 229920000728 polyester Polymers 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims description 7
- XPVIQPQOGTVMSU-UHFFFAOYSA-N (4-acetamidophenyl)arsenic Chemical compound CC(=O)NC1=CC=C([As])C=C1 XPVIQPQOGTVMSU-UHFFFAOYSA-N 0.000 claims abstract description 104
- 229920001225 polyester resin Polymers 0.000 claims abstract description 67
- 239000004645 polyester resin Substances 0.000 claims abstract description 67
- 229920013640 amorphous poly alpha olefin Polymers 0.000 claims abstract description 56
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 19
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 11
- 239000004034 viscosity adjusting agent Substances 0.000 claims abstract description 11
- -1 maleic anhydride modified APAO Chemical class 0.000 claims description 41
- 238000001816 cooling Methods 0.000 claims description 21
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 19
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 230000032050 esterification Effects 0.000 claims description 15
- 238000005886 esterification reaction Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 5
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- 238000003754 machining Methods 0.000 claims description 5
- 239000004005 microsphere Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims 40
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 16
- 230000001070 adhesive effect Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 229920006395 saturated elastomer Polymers 0.000 description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 229920000578 graft copolymer Chemical group 0.000 description 4
- 239000012943 hotmelt Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000009967 tasteless effect Effects 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
- 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
- C09J167/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
-
- 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
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention provides a kind of modified poly ester hot melt adhesive, are related to hot melt adhesive field, it is intended to solve the problems, such as in the prior art polyester hot-melt adhesive it is poor for applicability, for some materials bad adhesion comprising component A and B component, the component A comprise the following components in parts by weight：80-120 parts of polyester resin, 1-3 parts of antioxidant, the B component comprise the following components in parts by weight：5-15 parts of APAO, 14-30 parts of tackifying resins, 2-10 portions of viscosity modifiers and 12-23 parts of fillers.The present invention carries out blending and modifying to polyester resin hot melt adhesive system by APAO hot melt adhesive system, improves the cementitiousness and applicability of modified poly ester hot melt adhesive.
Description
Technical field
The present invention relates to hot melt adhesive fields more particularly to a kind of modified poly ester hot melt adhesive and preparation method thereof.
Background technique
Hot melt adhesive is a kind of adhesive of plasticity, its physical state changes with temperature and changed in certain temperature range
Become, and chemical characteristic is constant, it is non-toxic and tasteless, belong to environmental-protecting chemical product；It can be used for timber, plastics, fiber, fabric, gold
The mutual cementation such as category, furniture, lampshade, leather, craftwork, Toy electronics, appliance component, paper products, ceramics, EPE packaging
Body, usage amount is big, is widely used.
Currently, the Chinese invention patent that notification number is CN102703013A discloses a kind of Polyester hot-melt adhesive；Packet
Gum resin containing polyester hot melting, epoxy resin and curing agent, the polyester hot melting gum resin and epoxy resin and curing agent total amount
Mass ratio 70:30~99:1；Invention bonding force decaying is small, can not only be obviously improved polyester hot-melt adhesive to the bonding force of metal,
Reduce the melt viscosity of polyester hot-melt adhesive, improve polyester hot-melt adhesive at film outward appearance, and can prevent polyester hot-melt adhesive from hydrolyzing,
Excellent cementability is saved under low temperature, room temperature or even high temperature, production is high.
In this Polyester hot-melt adhesive, since epoxy resin contains various polarity group and active very big epoxy
Base, thus have very with the material of various polarities material, the especially high surface activity such as metal, glass, cement, timber, plastics
Strong bonding force, meanwhile, the cohesive strength of epoxy curing compound is also very big, and therefore, synthesis glue-joint strength is very high；But epoxy
The resin material small for polarity（Such as polyethylene, polypropylene, fluoroplastics）Bonding force is small, thus the incorporation of epoxy resin reduces
The adhesive property of polyester hot-melt adhesive.
Summary of the invention
The object of the present invention is to provide a kind of modified poly ester hot melt adhesive, have the advantages that applicability is wide, adhesive property is strong.
To achieve the above object, the present invention provides following technical solutions：
A kind of modified poly ester hot melt adhesive, including component A and B component, the component A comprise the following components in parts by weight：
80-120 parts of polyester resin
The B component comprises the following components in parts by weight：
5-15 parts of APAO
14-30 parts of tackifying resin
2-10 parts of viscosity modifier
12-23 parts of filler.
In above-mentioned technical proposal, polyester resin is as hot melt adhesive in use, its heat resistance with higher, good resistance to
Time, water resistance and excellent elasticity, still, in heating melting, viscosity is larger, either during processing or gluing,
It is more demanding to processing conditions and coated conditions, therefore, changed by incorporation good dispersion, the superior APAO hot melt adhesive of processing performance
The processing and practical performance of kind polyester resin；In addition, since APAO hot melt adhesive is polyolefins adhesive, to foamed plastics etc.
The small material of polarity has good bonding force, and after itself cooling therefore adhesive strength with higher is passing through APAO
After hot melt adhesive is blended with polyester resin, polyester resin hot melt adhesive can be improved to the adhesive property of various types of materials, it is improved and be applicable in
Property.
In some embodiments, the polyester resin be terephthalic acid (TPA), it is M-phthalic acid, 1,4-butanediol, two sweet
The polyester resin that alcohol is polymerized.
In above-mentioned technical proposal, the plastic polyester of heat, i.e. linear saturated polyester are formed by the polycondensation of binary acid and dihydric alcohol,
Its fusing point and glass transition temperature are higher, and hot melt adhesive obtained is heat-resist；From the point of view of molecular structure, the molecule straight chain of saturated polyester
Middle introducing phenyl will improve its fusing point, tensile strength and heat resistance, and melt viscosity, flexure will be improved by introducing alkyl and ehter bond
Property and flexibility, but this molecular structure also has high crystalline, and its wellability and glue-joint strength are poor, therefore, usually
Some other acids or alcohols need to be added in synthesis to replace a part of original monomer（Such as：1,4-butanediol）, make it
Atactic polymerization is carried out, to destroy high crystalline, improves wellability and glue-joint strength.
In some embodiments, the softening point of the polyester resin is 118-125 DEG C.
In above-mentioned technical proposal, by changing component proportion when polymerizeing, polyester tree of the softening point at 118-125 DEG C is obtained
Rouge hot melt adhesive improves the scope of application of polyester hot-melt adhesive.
In some embodiments, the APAO is the mixture of maleic anhydride modified APAO and silane-modified APAO.
In above-mentioned technical proposal, maleic anhydride is grafted on APAO chain and forms maleic anhydride modified APAO, on the one hand, horse
The grafting for carrying out acid anhydrides can not only improve the uniformity of the compatibility of each component and mixing in APAO hot melt adhesive, improve the processing of APAO
Quality, moreover it is possible to using maleic anhydride improve APAO adhesive property, on the other hand, maleic anhydride modified APAO with polyester resin
After mixing, the MAH of grafting is reacted with polyester resin terminal hydroxyl, and graft copolymer is formd on two-phase interface, is improved
Compatibility of the APAO hot melt adhesive in polyester resin, to improve the cohesive force and toughness of modified poly ester hot melt adhesive；In APAO
It is grafted reactive silane groups on polymer chain and forms silane-modified APAO, further increases APAO for the difficult bonding for adhering to ground material
Performance and thermal stability.
In some embodiments, the proportion of the maleic anhydride modified APAO and silane-modified APAO is 3:2.
It is same with polyester resin compatibility improving its own using maleic anhydride modified APAO in above-mentioned technical proposal
When, using maleic anhydride modified APAO as compatilizer, the compatibility of silane-modified APAO and polyester resin is improved, to improve
The adhesive property and toughness of modified poly ester hot melt adhesive.
In some embodiments, the propylene content of the maleic anhydride modified APAO is 65-70%, and softening point is
123-127℃。
In above-mentioned technical proposal, using the maleic anhydride modified APAO of high propylene content, improve the hot-fluid of APAO hot melt adhesive
Dynamic property and thermal stability.
In some embodiments, the propylene content of the silane-modified APAO is 80-85%, softening point 128-132
℃。
In above-mentioned technical proposal, softening point and maleic anhydride modified APAO close silane-modified APAO are selected, improves silicon
The consolute effect of alkane modified APAO and maleic anhydride modified APAO.
In some embodiments, viscosity of the polyester resin at 190 DEG C is 7500cps, and the maleic anhydride changes
Property viscosity of the APAO at 190 DEG C be 1500cps, viscosity of the silane-modified APAO at 190 DEG C is 3500cps.
Mobility in above-mentioned technical proposal, when improving polyester resin processing by the APAO system of low viscosity and use
Can, to reduce cost.
It in some embodiments, further include 1-3 parts of antioxidant.
By using above-mentioned technical proposal, antioxidant is mixed in modified poly ester hot melt adhesive, can not only be prevented modified poly-
The hot oxygen solution of ester hot melt adhesive, improves its thermal stability, moreover it is possible to which the toughness for improving modified poly ester hot melt adhesive extends it and uses the longevity
Life.
It is a further object to provide a kind of preparation methods of modified poly ester hot melt adhesive, can improve polyester resin
The blending effect of system and APAO system, to enhance the cementitiousness of modified poly ester hot melt adhesive.
To achieve the above object, the present invention provides following technical solutions：
A kind of preparation method of modified poly ester hot melt adhesive, includes the following steps：
S1：Binary acid, dihydric alcohol and catalyst are added in esterifying kettle by predetermined ratio and carry out esterification, reaction temperature is
175 DEG C~215 DEG C, when the amount that esterification distillates water is 97% or more of theoretical water yield, esterification terminates；
S2：Antioxidant is added in the product of S1, it is anti-that decompression polycondensation is carried out under conditions of 255~260 DEG C, 80~100Pa
1.5h is answered, polyester resin is obtained, pulverizes after cooling；
S3：Taking partial size is 1 × 10﹣ 6-9×10﹣ 6Mm microspheric silane-modified APAO and maleic anhydride modified APAO investment stirring
Kettle, temperature are controlled at 138-142 DEG C, mixing speed 20-40r/min, and stirring to silane-modified APAO is dispersed in Malaysia
In anhydride modified APAO, cooling discharging；
S4：The resulting APAO mixture of S3, tackifying resin, viscosity modifier and filler are put into kneading machine, warming while stirring
To 138-142 DEG C, mixing speed 35-45r/min, mixing time 25-30min, cooling discharging, and pulverize；
S5：It will be squeezed out in the resulting polyester resin powder of S2 and the resulting mixture powder investment double screw extruder of S4, it is described
The temperature of double screw extruder entrance, interlude and outlet section is controlled respectively in 115-125 DEG C, 135-145 DEG C, 125-130
℃；
S6：Hot-melt adhesive granules are formed by being granulated machining after the resulting extrudate room temperature cooling of S5.
In above-mentioned technical proposal, polyester resin hot melt adhesive is made by binary acid and dihydric alcohol, and in preparation APAO hot melt
When glue, higher melting-point nanoscale silane-modified APAO and maleic anhydride modified APAO is taken to be premixed first, obtained uniformly
Property preferable APAO mixture base-material, then other components in APAO mixture and B component are kneaded, it is excellent to obtain adhesive property
APAO hot melt adhesive, finally by double screw extruder realize polyester resin hot melt adhesive and APAO hot melt adhesive melt blending, into
And APAO hot melt adhesive is utilized to improve the cementitiousness of modified poly ester hot melt adhesive and be applicable in polyester resin hot melt adhesive System Modification
Property.
Compared with the prior art, the present invention has the following advantages：
1. carrying out blending and modifying to polyester resin hot melt adhesive system by APAO hot melt adhesive system, modified poly ester hot melt adhesive is improved
Cementitiousness and applicability；
2. improving the compatibility of each component in APAO hot melt adhesive system, and then improve by the incorporation of maleic anhydride modified APAO
The cementitiousness of APAO；
3. improving the adhesive property of modified poly ester hot melt adhesive and difficult sticky end material by the incorporation of silane-modified APAO.
Specific embodiment
Below by specific embodiment, technical scheme is described further.
Embodiment 1：
A kind of modified poly ester hot melt adhesive, including component A and B component, component A comprise the following components in parts by weight：
80 parts of polyester resin
1 part of antioxidant
B component comprises the following components in parts by weight：
5 parts of APAO
14 parts of tackifying resin
2 parts of viscosity modifier
12 parts of filler
Wherein, polyester resin is terephthalic acid (TPA), M-phthalic acid, 1,4-butanediol, two in this embodiment of the invention
The plastic polyester of heat that glycol is polymerized, i.e. linear saturated polyester, heat resistance with higher, good weather-proof, water resistance
With excellent elasticity；From the point of view of molecular structure, phenyl is introduced in the molecule straight chain of saturated polyester, its fusing point, anti-tensile will be improved
Intensity and heat resistance, melt viscosity, flexibility and flexibility, but the also high knot of this molecular structure will be improved by introducing alkyl and ehter bond
Crystalline substance, and its wellability and glue-joint strength are poor, therefore, usually some other acids or alcohols need to be added in synthesis to take
For a part of original monomer（Such as：1,4-butanediol）, so that it is carried out atactic polymerization, to destroy high crystalline, improve leaching
Lubricant nature and glue-joint strength；
And APAO is the mixture of maleic anhydride modified APAO and silane-modified APAO, and its proportion is 3:2, on the one hand, by horse
It is maleic anhydride grafted to forming maleic anhydride modified APAO on APAO chain, and the grafting of maleic anhydride can not only improve maleic anhydride and change
Property APAO and other components, the compatibility of APAO hot melt adhesive system and polyester resin hot melt adhesive system, the maleic anhydride of grafting
（MAH）It can also be reacted with the terminal hydroxyl of polyester resin, graft copolymer is formd on two-phase interface, improve APAO hot melt
The consolute effect of colloid system and polyester resin hot melt adhesive system enhances the cohesive force and toughness of modified poly ester hot melt adhesive；It is another
Reactive silane groups are grafted on APAO chain and form silane-modified APAO by aspect, are improved by introducing reactive silane groups
APAO hot melt adhesive system is for the difficult adhesive property and thermal stability for adhering to ground material；
The softening point of polyester resin is 118 DEG C, and the propylene content of maleic anhydride modified APAO is 65%, softening point is 123 DEG C, silicon
The propylene content of the modified APAO of alkane is 80%, softening point is 128 DEG C, polyester resin, the maleic anhydride for selecting softening point close to each other
Modified APAO and silane-modified APAO, facilitates processing, improves the consolute effect of each component；
Viscosity of the polyester resin at 190 DEG C is 7500cps, and viscosity of the maleic anhydride modified APAO at 190 DEG C is
The viscosity of 1500cps, silane-modified APAO at 190 DEG C is 3500cps, since polyester resin hot melt adhesive makes in the molten state
Used time viscosity is larger, and construction is more troublesome, and therefore, by mixing the lesser APAO hot melt adhesive system of viscosity, improves modified poly ester
The machinability and the mobility under molten condition of hot melt adhesive；
Antioxidant is 2,6- toluene di-tert-butyl phenol, and the addition of antioxidant can not only prevent the hot oxygen of modified poly ester hot melt adhesive
It decomposes, improves its thermal stability, moreover it is possible to improve modified poly ester hot melt adhesive toughness, prolong its service life；
Above-mentioned modified poly ester hot melt adhesive is prepared from the following steps,
S1：Binary acid, dihydric alcohol and catalyst are added in esterifying kettle by predetermined ratio and carry out esterification, reaction temperature is
175 DEG C, when the amount that esterification distillates water is 97% or more of theoretical water yield, esterification terminates；
S2：Antioxidant is added in the product of S1, depressurization condensation reaction 1.5h is carried out under conditions of 255 DEG C, 80Pa, is obtained
Polyester resin is pulverized after cooling；
S3：Taking partial size is 1 × 10﹣ 6Mm microspheric silane-modified APAO and maleic anhydride modified APAO put into stirred tank, temperature
At 138 DEG C, mixing speed 20r/min, stirring to silane-modified APAO is dispersed in maleic anhydride modified APAO for control,
Cooling discharging；
S4：The resulting APAO mixture of S3, tackifying resin, viscosity modifier and filler are put into kneading machine, warming while stirring
To 138 DEG C, mixing speed 35r/min, mixing time 25min, cooling discharging, and pulverize；
S5：It will be squeezed out in the resulting polyester resin powder of S2 and the resulting mixture powder investment double screw extruder of S4, double spiral shells
The temperature of bar extruder entrance, interlude and outlet section is controlled respectively at 115 DEG C, 135 DEG C, 125 DEG C；
S6：Hot-melt adhesive granules are formed by being granulated machining after the resulting extrudate room temperature cooling of S5.
Embodiment 2：
A kind of modified poly ester hot melt adhesive, including component A and B component, component A comprise the following components in parts by weight：
100 parts of polyester resin
2 parts of antioxidant
B component comprises the following components in parts by weight：
10 parts of APAO
20 parts of tackifying resin
6 parts of viscosity modifier
18 parts of filler
Wherein, polyester resin is terephthalic acid (TPA), M-phthalic acid, 1,4-butanediol, two in this embodiment of the invention
The plastic polyester of heat that glycol is polymerized, i.e. linear saturated polyester, heat resistance with higher, good weather-proof, water resistance
With excellent elasticity；From the point of view of molecular structure, phenyl is introduced in the molecule straight chain of saturated polyester, its fusing point, anti-tensile will be improved
Intensity and heat resistance, melt viscosity, flexibility and flexibility will be improved by introducing alkyl and ehter bond, but this molecular structure also has
High crystalline, and its wellability and glue-joint strength are poor, therefore, usually some other acids or alcohols need to be added in synthesis
To replace a part of original monomer（Such as：1,4-butanediol）, so that it is carried out atactic polymerization and mentioned to destroy high crystalline
High wellability and glue-joint strength；
And APAO is the mixture of maleic anhydride modified APAO and silane-modified APAO, and its proportion is 3:2, on the one hand, by horse
It is maleic anhydride grafted to forming maleic anhydride modified APAO on APAO chain, and the grafting of maleic anhydride can not only improve maleic anhydride and change
Property APAO and other components, the compatibility of APAO hot melt adhesive system and polyester resin hot melt adhesive system, the maleic anhydride of grafting
（MAH）It can also be reacted with the terminal hydroxyl of polyester resin, graft copolymer is formd on two-phase interface, improve APAO hot melt
The consolute effect of colloid system and polyester resin hot melt adhesive system enhances the cohesive force and toughness of modified poly ester hot melt adhesive；It is another
Reactive silane groups are grafted on APAO chain and form silane-modified APAO by aspect, are improved by introducing reactive silane groups
APAO hot melt adhesive system is for the difficult adhesive property and thermal stability for adhering to ground material；
The softening point of polyester resin is 120 DEG C, and the propylene content of maleic anhydride modified APAO is 66%, softening point is 125 DEG C, silicon
The propylene content of the modified APAO of alkane is 83%, softening point is 130 DEG C, polyester resin, the maleic anhydride for selecting softening point close to each other
Modified APAO and silane-modified APAO, facilitates processing, improves the consolute effect of each component；
Viscosity of the polyester resin at 190 DEG C is 7500cps, and viscosity of the maleic anhydride modified APAO at 190 DEG C is
The viscosity of 1500cps, silane-modified APAO at 190 DEG C is 3500cps, since polyester resin hot melt adhesive makes in the molten state
Used time viscosity is larger, and construction is more troublesome, and therefore, by mixing the lesser APAO hot melt adhesive system of viscosity, improves modified poly ester
The machinability and the mobility under molten condition of hot melt adhesive；
Antioxidant is 2,6- toluene di-tert-butyl phenol, and the addition of antioxidant can not only prevent the hot oxygen of modified poly ester hot melt adhesive
It decomposes, improves its thermal stability, moreover it is possible to improve modified poly ester hot melt adhesive toughness, prolong its service life；
Above-mentioned modified poly ester hot melt adhesive is prepared from the following steps,
S1：Binary acid, dihydric alcohol and catalyst are added in esterifying kettle by predetermined ratio and carry out esterification, reaction temperature is
200 DEG C, when the amount that esterification distillates water is 97% or more of theoretical water yield, esterification terminates；
S2：Antioxidant is added in the product of S1, depressurization condensation reaction 1.5h is carried out under conditions of 257 DEG C, 90Pa, is obtained
Polyester resin is pulverized after cooling；
S3：Taking partial size is 6 × 10﹣ 6Mm microspheric silane-modified APAO and maleic anhydride modified APAO put into stirred tank, temperature
At 140 DEG C, mixing speed 30r/min, stirring to silane-modified APAO is dispersed in maleic anhydride modified APAO for control,
Cooling discharging；
S4：The resulting APAO mixture of S3, tackifying resin, viscosity modifier and filler are put into kneading machine, warming while stirring
To 140 DEG C, mixing speed 40r/min, mixing time 27min, cooling discharging, and pulverize；
S5：It will be squeezed out in the resulting polyester resin powder of S2 and the resulting mixture powder investment double screw extruder of S4, it is described
The temperature of double screw extruder entrance, interlude and outlet section is controlled respectively at 120 DEG C, 140 DEG C, 127 DEG C；
S6：Hot-melt adhesive granules are formed by being granulated machining after the resulting extrudate room temperature cooling of S5.
Embodiment 3：
A kind of modified poly ester hot melt adhesive, including component A and B component, component A comprise the following components in parts by weight：
120 parts of polyester resin
3 parts of antioxidant
B component comprises the following components in parts by weight：
15 parts of APAO
30 parts of tackifying resin
10 parts of viscosity modifier
23 parts of filler
Wherein, polyester resin is terephthalic acid (TPA), M-phthalic acid, 1,4-butanediol, two in this embodiment of the invention
The plastic polyester of heat that glycol is polymerized, i.e. linear saturated polyester, heat resistance with higher, good weather-proof, water resistance
With excellent elasticity；From the point of view of molecular structure, phenyl is introduced in the molecule straight chain of saturated polyester, its fusing point, anti-tensile will be improved
Intensity and heat resistance, melt viscosity, flexibility and flexibility will be improved by introducing alkyl and ehter bond, but this molecular structure also has
High crystalline, and its wellability and glue-joint strength are poor, therefore, usually some other acids or alcohols need to be added in synthesis
To replace a part of original monomer（Such as：1,4-butanediol）, so that it is carried out atactic polymerization and mentioned to destroy high crystalline
High wellability and glue-joint strength；
And APAO is the mixture of maleic anhydride modified APAO and silane-modified APAO, and its proportion is 3:2, on the one hand, by horse
It is maleic anhydride grafted to forming maleic anhydride modified APAO on APAO chain, and the grafting of maleic anhydride can not only improve maleic anhydride and change
Property APAO and other components, the compatibility of APAO hot melt adhesive system and polyester resin hot melt adhesive system, the maleic anhydride of grafting
（MAH）It can also be reacted with the terminal hydroxyl of polyester resin, graft copolymer is formd on two-phase interface, improve APAO hot melt
The consolute effect of colloid system and polyester resin hot melt adhesive system enhances the cohesive force and toughness of modified poly ester hot melt adhesive；It is another
Reactive silane groups are grafted on APAO chain and form silane-modified APAO by aspect, are improved by introducing reactive silane groups
APAO hot melt adhesive system is for the difficult adhesive property and thermal stability for adhering to ground material；
The softening point of polyester resin is 125 DEG C, and the propylene content of maleic anhydride modified APAO is 70%, softening point is 127 DEG C, silicon
The propylene content of the modified APAO of alkane is 85%, softening point is 132 DEG C, polyester resin, the maleic anhydride for selecting softening point close to each other
Modified APAO and silane-modified APAO, facilitates processing, improves the consolute effect of each component；
Viscosity of the polyester resin at 190 DEG C is 7500cps, and viscosity of the maleic anhydride modified APAO at 190 DEG C is
The viscosity of 1500cps, silane-modified APAO at 190 DEG C is 3500cps, since polyester resin hot melt adhesive makes in the molten state
Used time viscosity is larger, and construction is more troublesome, and therefore, by mixing the lesser APAO hot melt adhesive system of viscosity, improves modified poly ester
The machinability and the mobility under molten condition of hot melt adhesive；
Antioxidant is 2,6- toluene di-tert-butyl phenol, and the addition of antioxidant can not only prevent the hot oxygen of modified poly ester hot melt adhesive
It decomposes, improves its thermal stability, moreover it is possible to improve modified poly ester hot melt adhesive toughness, prolong its service life；
Above-mentioned modified poly ester hot melt adhesive is prepared from the following steps,
S1：Binary acid, dihydric alcohol and catalyst are added in esterifying kettle by predetermined ratio and carry out esterification, reaction temperature is
215 DEG C, when the amount that esterification distillates water is 97% or more of theoretical water yield, esterification terminates；
S2：Antioxidant is added in the product of S1, depressurization condensation reaction 1.5h is carried out under conditions of 260 DEG C, 100Pa, is obtained
To polyester resin, pulverize after cooling；
S3：Taking partial size is 9 × 10﹣ 6Mm microspheric silane-modified APAO and maleic anhydride modified APAO put into stirred tank, temperature
At 142 DEG C, mixing speed 40r/min, stirring to silane-modified APAO is dispersed in maleic anhydride modified APAO for control,
Cooling discharging；
S4：The resulting APAO mixture of S3, tackifying resin, viscosity modifier and filler are put into kneading machine, warming while stirring
To 142 DEG C, mixing speed 45r/min, mixing time 30min, cooling discharging, and pulverize；
S5：It will be squeezed out in the resulting polyester resin powder of S2 and the resulting mixture powder investment double screw extruder of S4, it is described
The temperature of double screw extruder entrance, interlude and outlet section is controlled respectively at 125 DEG C, 145 DEG C, 130 DEG C；
S6：Hot-melt adhesive granules are formed by being granulated machining after the resulting extrudate room temperature cooling of S5.
The present invention is guaranteed using the peel strength of GB/T2790-1995 measurement modified poly ester hot melt adhesive by peel strength
Its adhesive property, stiff adherend select PP plate and ABS plate respectively, and flexible adherend all selects lining cloth.
It is detected, is obtained as follows by the modified poly ester hot melt adhesive and blank test group that disclose above-mentioned 3 embodiments
Test result in table 1：
Table 1
Blank test group：Polyester hot-melt adhesive made from 100 parts of polyester resin and 2 parts of antioxidant.
By above-mentioned testing result：Polyester resin hot melt adhesive system is mixed by APAO hot melt adhesive system to be blended
It is modified, the applicability of polyester resin hot melt adhesive can not only be improved, also from the peel strength measured it is found that its adhesion strength is changed
It is kind, especially implement 2 resulting modified poly ester hot melt adhesive.
This specific embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the art
Member can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as at this
All by the protection of Patent Law in the scope of the claims of invention.
Claims (10)
1. a kind of modified poly ester hot melt adhesive, which is characterized in that including component A and B component, the component A includes following parts by weight
Component：
80-120 parts of polyester resin
The B component comprises the following components in parts by weight：
5-15 parts of APAO
14-30 parts of tackifying resin
2-10 parts of viscosity modifier
12-23 parts of filler.
2. a kind of modified poly ester hot melt adhesive according to claim 1, which is characterized in that the polyester resin is terephthaldehyde
The polyester resin that acid, M-phthalic acid, 1,4- butanediol, diethylene glycol (DEG) are polymerized.
3. a kind of modified poly ester hot melt adhesive according to claim 2, which is characterized in that the softening point of the polyester resin
It is 118-125 DEG C.
4. a kind of modified poly ester hot melt adhesive according to claim 3, which is characterized in that the APAO is maleic anhydride modified
The mixture of APAO and silane-modified APAO.
5. a kind of modified poly ester hot melt adhesive according to claim 4, which is characterized in that the maleic anhydride modified APAO and
The proportion of silane-modified APAO is 3:2.
6. a kind of modified poly ester hot melt adhesive according to claim 5, which is characterized in that the maleic anhydride modified APAO's
Propylene content is 65-70%, and softening point is 123-127 DEG C.
7. a kind of modified poly ester hot melt adhesive according to claim 6, which is characterized in that the propylene of the silane-modified APAO
Content is 80-85%, and softening point is 128-132 DEG C.
8. a kind of modified poly ester hot melt adhesive according to claim 7, which is characterized in that the polyester resin is at 190 DEG C
Viscosity be 7500cps, viscosity of the maleic anhydride modified APAO at 190 DEG C be 1500cps, the silane-modified APAO
Viscosity at 190 DEG C is 3500cps.
9. a kind of modified poly ester hot melt adhesive according to claim 8, which is characterized in that further include 1-3 parts of antioxidant.
10. the preparation method of modified poly ester hot melt adhesive described in a kind of claim 9, which is characterized in that include the following steps：
S1：Binary acid, dihydric alcohol and catalyst are added in esterifying kettle by predetermined ratio and carry out esterification, reaction temperature is
175 DEG C~215 DEG C, when the amount that esterification distillates water is 97% or more of theoretical water yield, esterification terminates；
S2：Antioxidant is added in the product of S1, it is anti-that decompression polycondensation is carried out under conditions of 255~260 DEG C, 80~100Pa
1.5h is answered, polyester resin is obtained, pulverizes after cooling；
S3：Taking partial size is 1 × 10﹣ 6-9×10﹣ 6Mm microspheric silane-modified APAO and maleic anhydride modified APAO investment stirring
Kettle, temperature are controlled at 138-142 DEG C, mixing speed 20-40r/min, and stirring to silane-modified APAO is dispersed in Malaysia
In anhydride modified APAO, cooling discharging；
S4：The resulting APAO mixture of S3, tackifying resin, viscosity modifier and filler are put into kneading machine, warming while stirring
To 138-142 DEG C, mixing speed 35-45r/min, mixing time 25-30min, cooling discharging, and pulverize；
S5：It will be squeezed out in the resulting polyester resin powder of S2 and the resulting mixture powder investment double screw extruder of S4, it is described
The temperature of double screw extruder entrance, interlude and outlet section is controlled respectively in 115-125 DEG C, 135-145 DEG C, 125-130
℃；
S6：Hot-melt adhesive granules are formed by being granulated machining after the resulting extrudate room temperature cooling of S5.
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| CN110591626A (en) * | 2019-08-28 | 2019-12-20 | 苏州德圣辉新能源科技有限公司 | Repair glue with good waterproof effect for solar backboard |
| CN114412328A (en) * | 2022-01-21 | 2022-04-29 | 广州市盛艺门业有限公司 | Composite solid wood door |
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| CN108865036B (en) | 2020-10-20 |
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Address after: Shanghai Road, Binjiang fine chemical industry park, Qidong Economic Development Zone, Nantong City, Jiangsu Province, 226200 Patentee after: Qidong Xintianding Material Technology Co.,Ltd. Country or region after: China Address before: Shanghai Road, Binjiang fine chemical industry park, Qidong Economic Development Zone, Nantong City, Jiangsu Province, 226200 Patentee before: QIDONG XINTIANDING HOT MELT ADHESIVE Co.,Ltd. Country or region before: China |