CN104673177B - Polyamide thermoplastic hot-melt adhesive composition - Google Patents
Polyamide thermoplastic hot-melt adhesive composition Download PDFInfo
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- CN104673177B CN104673177B CN201310630079.1A CN201310630079A CN104673177B CN 104673177 B CN104673177 B CN 104673177B CN 201310630079 A CN201310630079 A CN 201310630079A CN 104673177 B CN104673177 B CN 104673177B
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Abstract
The present invention relates to a kind of polyamide thermoplastic hot-melt adhesive composition, it is included：A) the amine type copolyamide of 5~90 weight % rings two, b) 5 90 weight % polyether polyamine type copolyamides, and c) 1 10 weight % polymer-wax, on the basis of the gross weight of polyamide thermoplastic hot-melt adhesive composition.Hot-melt adhesive composition of the present invention has excellent adhesive property to metallic aluminium and radiant crosslinked polyethylene plate, while the open hour are shorter, quick solidifying, improve production efficiency.
Description
Technical field
The present invention relates to polyamide thermoplastic hot-melt adhesive composition, more particularly to handing over metallic aluminium and radiation
Connection polyethylene board has the plastic polyamide hot-melt adhesive composition of superior adhesion energy.
Background technology
Polyamide as adhesive mainly has two classes, and molecular weight is higher for copolyamide, this kind of polyamide hot melt
Glue has excellent water-fastness and dry cleaning resistance energy, is widely used in the bonding of fiber, very big in textile industry dosage.It is another
Class polyamide is formed by dimeric dibasic acid and diamine polycondensation, has the advantages that narrow melting range, quick solidifying, adhesive property are excellent,
It is now widely used for the fields such as shoemaking, automobile, electronics, material contracting with heat.
Research for polyamide adhesives both at home and abroad has had a lot, the improvement especially to dimer acid type polyamide,
By using the mode of blending or copolymerization, the shortcomings of its fragility, easy moisture absorption, is improved., will be poly- in US4670552 patents
Acid amides and polyesteramide blending, obtained it is a kind of there is the flexible PUR of high and low temperature, to polyethylene, polyester, polyamide with
And the material such as PVC has good bonding；US5989385 by dimeric acid type polyamide hot melt adhesive and rosin resin, terpene resin,
EVA etc. is blended, and obtains a kind of PUR, applies in terms of bookbinding, can carry out books dress at relatively low temperature
Order.In recent years, the domestic research for dimer acid type polyamide also result in the attention of professional.CN101372610 passes through
Introduce the oligomer such as polyethylene oxide diamine or propylene oxide diamines to be modified, compared to traditional dimer acid type polyamide, its toughness
It is greatly improved, it is low temperature resistant to reach less than -40 DEG C；CN101633829 improves polyamides by introducing active nitrile rubber
The sealing of amine adhesive, it is allowed to be widely used in heat-shrinkable T bush.
Dimeric acid type polyamide hot melt adhesive is constantly expanding due to excellent performance, application field.But single use
Dimer acid type polyamide is as adhesive, and in the occasion of some particular/special requirements, performance still has some defects, especially one
Under a little dynamic use conditions, under the conditions of being converted such as high and low temperature alternative, toughness, adhesive property and sealing property will persistently keep good
Good state, this is difficult to accomplish for single dimer acid type polyamide.So need to integrate the performance of different copolymer acid amides,
To reach the high adhesive of comprehensive performance.
Therefore, it is good there is an urgent need to a kind of adhesive property in this area while the open hour are shorter, quick solidifying and production efficiency
High polyamide binder.
The content of the invention
The present invention is by by two kinds of copolyamide melt blendings, obtaining a kind of polyamide Adhesive composition, combining not
The advantages of polyamide adhesive obtained with comonomer, at the same avoid due in single copolyamide comonomer it is excessive and
The shortcomings that open hour brought are long.
Therefore, the invention provides a kind of polyamide thermoplastic hot-melt adhesive composition, it is included：
A) the amine type dimeric dibasic acid copolyamide of 5~90 weight % rings two,
B) 5-90 weight % polyether polyamines type dimeric dibasic acid copolyamide, and
C) 1-10 weight % polymer-wax, on the basis of the gross weight of polyamide thermoplastic hot-melt adhesive composition.
Compared to the dimer acid type polyamide adhesive of exclusive use, the polyamide thermosol composition has to nonpolar material
The bonding of material and polar material greatly improves, and has good sealing, water absorption rate pole to the polyethylene base material of heat-shrinkable T bush
Low, ageing-resistant performance is excellent, can be applicable to the harsh occasion of temperature checker, requirement.Compared to single copolyamide,
Hardening time is short, saves the applying glue time.It is easy to industrialized production.
Embodiment
In one preferred embodiment, the invention provides a kind of polyamide thermoplastic hot-melt adhesive composition,
It is included：
A) the amine type dimeric dibasic acid copolyamide of 10~85 weight %5-6 yuan of rings two,
B) 10-85 weight % polyether polyamines type dimeric dibasic acid copolyamide, and
C) 2-8 weight % polymer-wax, on the basis of the gross weight of polyamide thermoplastic hot-melt adhesive composition.
In a preferred embodiment, the above-mentioned amine type dimeric dibasic acid copolyamide of 5-6 yuan of rings two includes：
(1) dicarboxylic acids copolymerization units, it includes：
(a) 70~90 moles of % dimeric dibasic acid copolymerization units, and
(b) 10~30 moles of %C2-C14Aliphatic dicarboxylic acid copolymerization units, with the total moles of dicarboxylic acids copolymerization units
On the basis of number；And
(2) diamine copolymerization units, it includes：
(c) 50~70 moles of %C2-C8Linear aliphatic diamines unit；With
(d) 30~50 moles of %5-6 yuan of rings diamines units, on the basis of the total mole number of diamine copolymerization units；
The number-average molecular weight Mn of the amine type dimeric dibasic acid copolyamide of 5-6 yuan of rings two is 5000~40000；Preferably 10000-30000.
In a preferred embodiment, above-mentioned polyether polyamine type dimeric dibasic acid copolyamide includes：
(1) dicarboxylic acids copolymerization units, it includes：
(a) 70~90 moles of % dimeric dibasic acid copolymerization units, and
(b) 10~30 moles of %C2-C14Aliphatic dicarboxylic acid copolymerization units, with the total moles of dicarboxylic acids copolymerization units
On the basis of number；And
(2) diamine copolymerization units, it includes：
(c) 30~50 moles of %C2-C8Linear aliphatic diamines unit；With
(d) 50~70 moles of % polyether polyamine copolymerization units, on the basis of the total mole number of diamine copolymerization units；This is poly-
The number-average molecular weight Mn of ether polyamine type dimeric dibasic acid copolyamide is 2000~20000；Preferably 5000-10000.
Polyamide thermoplastic hot melt adhesive composition of the present invention is by the Hes of two amine type dimeric dibasic acid copolyamide PA of 5-6 yuan of rings I
Other auxiliary agent melt blendings such as polyether polyamine type dimeric dibasic acid copolyamide PA II and polymer-wax obtain.
The above-mentioned amine type dimeric dibasic acid copolyamide component PA I of 5-6 yuan of rings two is by dimeric dibasic acid and optional C6-C14Aliphatic two
First carboxylic acid and C2-C8The comonomer copolycondensation such as straight-chain aliphatic diamines and 5-6 yuan of rings diamines obtains.
Above-mentioned polyether polyamine type dimeric dibasic acid copolyamide PA II is by dimeric dibasic acid and optional C6-C14Aliphatic dicarboxylic acid
With C2-C8The comonomer copolycondensation such as straight-chain aliphatic diamines and polyether polyamine obtains.
Contained dimeric dibasic acid is total in above-mentioned the amine type copolyamide PA I of 5-6 yuan of rings two and polyether polyamine type copolyamide PA II
Poly- unit is by C16~20What the dimerization syntaxy of unrighted acid obtained.Above-mentioned dimeric dibasic acid is, for example, by linoleic acid, oil
Acid, leukotrienes, elaidic acid, behenic acid, eleostearic acid or dimeric dibasic acid derived from appropriate youngster's oil.Preferably C18The two of unrighted acid
Polyacids, for example, the dimeric dibasic acid obtained by dimerization such as appropriate youngster's oil, linoleic acid, oleic acid or leukotrienes.Dimeric dibasic acid is for example including dimerization
Linoleic acid, dimerization oleic acid, dimerization leukotrienes, dimerization elaidic acid, dimerization behenic acid, dimerization eleostearic acid or their mixture.
For preparing the amine type copolyamide PA I of 5-6 yuan of rings two and polyether polyamine type copolyamide PA II dimer acid material
It is required that dimerization acid content, in more than 65wt%, preferably 75~95wt%, preferred dimerization constituent content is in 90~97wt%；Three
Acid content is in below 15wt%, preferably 3~10wt%；Below mono-acid content 5wt%, preferred content is in 1~3wt%.Dimeric dibasic acid
It can buy on the market.
Contained by above-mentioned the amine type dimeric dibasic acid copolyamide PA I of 5-6 yuan of rings two and polyether polyamine type dimeric dibasic acid copolyamide PA II
C2-C14Aliphatic dicarboxylic acid copolymerization units are C2-C14Derived from aliphatic dicarboxylic acid.Preferable aliphatic dicarboxylic acid
It is C4-C12Straight-chain aliphatic dicarboxylic acids, more preferably C6-C10Straight-chain aliphatic dicarboxylic acids.Above-mentioned binary aliphatic
Carboxylic acid is for example including ethanedioic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, ten
One carbon dicarboxylic acid, ten binary binary acid, ten ternary binary acid, 15 yuan of dicarboxylic acids, ten hexa-atomic dicarboxylic acids or theirs is mixed
Compound.Preferable example is azelaic acid, decanedioic acid or their mixture.
Contained by above-mentioned the amine type dimeric dibasic acid copolyamide PA I of 5-6 yuan of rings two and polyether polyamine type dimeric dibasic acid copolyamide PA II
C2-C8Linear aliphatic diamines unit is by C2-C8Aliphatic diamine is derived.Above-mentioned aliphatic diamine for example wraps
Include ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, heptamethylene diamine, pentanediamine, 2 methyl pentamethylenediamine, octamethylenediamine or their mixing
Thing.Preferable aliphatic diamine is for example including ethylenediamine, propane diamine, butanediamine, hexamethylene diamine or its mixture, preferred aliphatic series
Diamine is for example including ethylenediamine, hexamethylene diamine or its mixture.
Ring diamines unit contained by the above-mentioned amine type dimeric dibasic acid copolyamide PA I of 5-6 yuan of rings two is as derived from ring diamines.
Described ring diamines includes alicyclic diamine, aromatic ring diamines, heterocyclic diamine or their mixture.Preferable ring diamines is containing 5-
The ring diamines of 6 yuan of alicyclic rings, aromatic ring or azacyclo-.The nitrogen-atoms of the amine of formation may be embodied in ring, may be alternatively located at ring outside chain
On.Above-mentioned ring diamines is for example including piperazine, imidazoline, aminoethyl piperazine, 1,4- bis- (3- aminopropyls) piperazine, hexamethylene two
Amine, cyclohexyl are to dimethylamine, different Fu Er ketone diamines, lupetazin, benzene methanediamine, pyridine diamines etc., one of which or it is mixed
Compound, preferably cyclohexyl diamine, lupetazin, piperazine etc., more preferably piperazine.
Polyether polyamine copolymerization units contained by above-mentioned polyether polyamine type dimeric dibasic acid copolyamide PA II are derived by polyether polyamine
And obtain.Above-mentioned polyether polyamine includes having 2-5, the polyethers of preferably 2-3 Amino End Group, and molecular weight is generally 150~
4000, preferably 200~2000.
Above-mentioned polyether polyamine is for example including polyethyleneoxide diamine, polyoxyethylene triamine, polypropyleneoxide diamine, polyoxypropylene three
Amine, polybutylene diamines, polybutylene triamine, poly- (1,2)-dimethyl oxygen ethylene diamine, poly- (1,2)-dimethyl oxygen ethene three
Amine or their mixture, the preferable trade mark have polyetheramine D-230, polyetheramine D-400, polyetheramine D-2000 or polyetheramine T-
One kind or any several mixtures in 403.
Trade name D-230, D-400 and D-2000 polyether polyamine can use following molecular formula to represent：
Wherein for D-230, x ≈ 2.5；For D-400, x ≈ 6.1；For D-2000, x ≈ 34.
Trade name T-430 polyether polyamine can use following molecular formula to represent：
General 120~240 DEG C of the reaction temperature of above-mentioned copolycondensation, reacted between 120~140 DEG C during beginning, so
When temperature gradually being risen into 230~240 DEG C afterwards, carry out polycondensation reaction is vacuumized.
In a particularly preferred embodiment, the above-mentioned amine type dimeric dibasic acid copolyamide PAI of 5-6 yuan of rings two for example by
Following method is made：By the dimeric dibasic acid after weighing, C2-C14Aliphatic dicarboxylic acid, C2-C8Linear aliphatic diamines, ring diamines and
A small amount of antioxidant etc. loads in 2000ml four-hole boiling flasks, and wherein the total moles ratio of dimeric dibasic acid and diamines is 1：(0.95~1.10),
Nitrogen is passed through into four-hole boiling flask, temperature in the reaction bulb is heated to 120-140 DEG C, mixes various raw materials melts in reaction bulb
Close, reaction temperature is slowly lifted by 20 DEG C/h of programming rates, until being increased to 230~240 DEG C, keep the temperature section at least 1
Hour, and the water distillated is measured, when reaching the 80% of theoretical amount, decompression step by step can be carried out；Finally complete under a high vacuum whole
Reaction, the polyamide sample of HMW is made；Finally polyamide is fallen in tetrafluoro plate face while hot, grain is cut into after cooling and shaping
Son.
In another particularly preferred embodiment, above-mentioned polyether polyamine type dimeric dibasic acid copolyamide PAII for example by
Following method is made：By the dimeric dibasic acid after weighing, C2-C14Aliphatic dicarboxylic acid, C2-C8Linear aliphatic diamines, polyether polyamine with
And a small amount of antioxidant etc. loads in 2000ml four-hole boiling flasks, wherein the mol ratio of dimeric dibasic acid and diamines is 1：(0.95~1.10),
Nitrogen is passed through into four-hole boiling flask, temperature in the reaction bulb is heated to 120-140 DEG C, mixes various raw materials melts in reaction bulb
Close, reaction temperature is slowly lifted by 20 DEG C/h of programming rates, until being increased to 230~240 DEG C, keep the temperature section at least 1
Hour, and the water distillated is measured, when reaching the 80% of theoretical amount, decompression step by step can be carried out；Finally complete under a high vacuum whole
Reaction, the polyamide sample of HMW is made；Finally polyamide is fallen in tetrafluoro plate face while hot, grain is cut into after cooling and shaping
Son.
Then, the amine type dimeric dibasic acid copolyamide PAI of 5-6 yuan of rings two obtained above, polyether polyamine type dimeric dibasic acid are copolymerized
Acid amides PAII and polymer-wax weigh, and are put into a twin-screw or banbury the banburying 10-30 minutes at 120-140 DEG C, obtain
To the polyamide thermoplastic hot-melt adhesive composition of the present invention.
Contained polymer-wax includes polyamide wax, polyethylene in polyamide thermoplastic hot-melt adhesive composition of the present invention
Wax, acrylate wax or their mixture.The number-average molecular weight of polymer-wax is in 1000-5000, preferably 2000-4000.
The softening point of polyamide thermoplastic hot-melt adhesive composition of the present invention can adjust in wider scope, applicability
Extensively, viscosity is low, easy to process；And it is excellent to the adhesive property of metal and difficult viscous plastic, the open hour are short, quick solidifying.Can
Applied to various bonding fields.
Can be commonly used in the art anti-that can add on a small quantity in polyamide thermoplastic hot-melt adhesive composition of the present invention
Oxygen agent, anti ultraviolet agent, nucleator, impact modifier, lubricant etc..
Inventor also found in further application test, compared to exclusive use dimer acid polyamide hotmelt, sheet
Invention polyamide thermoplastic hot-melt adhesive composition effectively increases hardening time, while other performances also have synergy,
Adhesive property and mobility increase than single polyamide hot.And each component compatibility in composition
It is good, without the phenomenon of split-phase.
Polyamide thermoplastic hot-melt adhesive composition softening point range of the present invention is at 110 DEG C~180 DEG C, 200 DEG C
Melt viscosity is in 2000~15000cp, preferably 5000-12000cp.Through to metal Al and the survey of radiant crosslinked polyethylene plate
Examination, has excellent adhesive property.The open hour are shorter simultaneously, quick solidifying, improve production efficiency.
Embodiment
Examples below is used to further illustrate the present invention, it is to be understood that these embodiments cannot be used for limiting this hair
Bright protection domain.
In the following example, the performance parameter of polyamide thermosol adhesive of the present invention is determined as follows.
Softening point is tested：Tested by standard GB/T 15332-94.
Melt viscosity is tested：Glued using Brookfield DV-E type rotation viscometer test samples in 232 DEG C of melting
Degree.
Open hour test：Tested according to standard HG/T 3716-2003.
Adhesive strength is tested：
Bondings of the PE to PE：A width of 25mm PE materials are placed on thermal-flame quick calcination to PE material softenings, so
The polyamide hot of melting is applied on PE calcination faces afterwards, the PE quick-bindings of gluing will be applied, cooling, be placed under test condition
After 12h, peel strength performance test is carried out in model GT-AI-3000 tensile testing machines.
Bondings of the Al to Al：The aluminum flake surface that a width of length is 100mm, wide 25mm, thickness are 1mm is wiped with acetone
Only, then the polyamide hot of melting is applied on surface-treated aluminium flake, another aluminium flake quick-binding, cools down, put
Under 10 kgf pressure, after room temperature places 12h, peel strength performance survey is carried out in model GT-AI-3000 tensile testing machines
Examination.
Preparation example PA I -1
By 0.4mol dimeric dibasic acids (trade mark P1013, big purchased from U.S.'s standing grain), 0.1mol azelaic acids, 0.3mol hexamethylene diamines,
In 0.2mol piperazines and a small amount of 5.2g antioxidant 1010s input 2000ml four-hole boiling flasks, 130 DEG C are warming up under nitrogen protection；
After component is completely dissolved in bottle, start slowly heating.240 DEG C were warming up in 1.5~2 hours；Measure water yield；It is to be achieved
Theoretical water yield more than 80% when, carry out decompression step by step；Whole reaction is finally completed under a high vacuum, and the vacuum reaction time is about
5~10 hours.Then with nitrogen pressurising to normal pressure, half an hour is stirred.Finally polyamide is fallen in tetrafluoro plate face while hot, it is cold
But particle is cut into after being molded.
Obtained polyamide hot, after tested, ring and ball softening point are 140 DEG C；Melt viscosity is 12000cp at 200 DEG C.
Preparation example PA I -2
By 0.4mol dimeric dibasic acids (trade mark P1013, big purchased from U.S.'s standing grain), 0.1mol azelaic acids, 0.3mol ethylenediamines,
In 0.2mol aminoethyl piperazines and a small amount of 5.4g antioxidant 1010s input 2000ml four-hole boiling flasks, it is warming up under nitrogen protection
130℃；After component is completely dissolved in bottle, start slowly heating.240 DEG C were warming up in 1.5~2 hours；Measure water yield；
Theoretical water yield to be achieved more than 80% when, carry out decompression step by step；Whole reaction, vacuum reaction are finally completed under a high vacuum
About 5~10 hours time.Then with nitrogen pressurising to normal pressure, half an hour is stirred.Finally polyamide is fallen in tetrafluoro plate while hot
On face, particle is cut into after cooling and shaping.
Obtained polyamide hot, after tested, ring and ball softening point are 135 DEG C；Melt viscosity is 11000cp at 200 DEG C.
Preparation example PA I -3
By 0.4mol dimeric dibasic acids (trade mark P1013, big purchased from U.S.'s standing grain), 0.1mol azelaic acids, 0.3mol ethylenediamines,
In (3- aminopropyls) piperazine of 0.2mol1,4- bis- and a small amount of 5.5g antioxidant 1010s input 2000ml four-hole boiling flasks, protected in nitrogen
130 DEG C are warming up under shield；After component is completely dissolved in bottle, start slowly heating.240 DEG C were warming up in 1.5~2 hours；
Measure water yield；Theoretical water yield to be achieved more than 80% when, carry out decompression step by step；Finally complete under a high vacuum whole anti-
Should, about 5~10 hours vacuum reaction time.Then with nitrogen pressurising to normal pressure, half an hour is stirred.Finally while hot by polyamide
In in tetrafluoro plate face, particle is cut into after cooling and shaping.
Obtained polyamide hot, after tested, ring and ball softening point are 130 DEG C；Melt viscosity is 9500cp at 200 DEG C.
Preparation example PA I -4
By 0.4mol dimeric dibasic acids (trade mark P1013, big purchased from U.S.'s standing grain), 0.1mol azelaic acids, 0.3mol ethylenediamines,
0.2mol in benzene methanediamine and 5.5g antioxidant 1010s input 2000ml four-hole boiling flasks, being warming up to 130 under nitrogen protection
℃；After component is completely dissolved in bottle, start slowly heating.240 DEG C were warming up in 1.5~2 hours；Measure water yield；Treat
When reaching more than the 80% of theoretical water yield, decompression step by step is carried out；Whole reaction is finally completed under a high vacuum, during vacuum reaction
Between about 5~10 hours.Then with nitrogen pressurising to normal pressure, half an hour is stirred.Finally polyamide is fallen in tetrafluoro plate face while hot
On, particle is cut into after cooling and shaping.
Obtained polyamide hot, after tested, ring and ball softening point are 145 DEG C；Melt viscosity is 7500cp at 200 DEG C.
Preparation example PA II -1
By 0.4mol dimeric dibasic acids (trade mark P1013, big purchased from U.S.'s standing grain), 0.1mol decanedioic acid, 0.2mol ethylenediamines,
In 0.3mol polyetheramine D-400 and 5.5g antioxidant 1010 input 2000ml four-hole boiling flasks, 130 are warming up under nitrogen protection
℃；After component is completely dissolved in bottle, start slowly heating.240 DEG C were warming up in 1.5~2 hours；Measure water yield；Treat
When reaching more than the 80% of theoretical water yield, decompression step by step is carried out；Whole reaction is finally completed under a high vacuum, during vacuum reaction
Between about 5~10 hours.Then with nitrogen pressurising to normal pressure, half an hour is stirred.Finally polyamide is fallen in tetrafluoro plate face while hot
On, particle is cut into after cooling and shaping.
Obtained polyamide hot, after tested, ring and ball softening point are 135 DEG C；Melt viscosity is 7000cp at 200 DEG C.
Preparation example PA II -2
By 0.4mol dimeric dibasic acids (trade mark P1013, big purchased from U.S.'s standing grain), 0.1mol decanedioic acid, 0.4mol ethylenediamines,
In 0.1mol polyetheramine D-2000 and 6.6g antioxidant 1010 input 2000ml four-hole boiling flasks, it is warming up under nitrogen protection
130℃；After component is completely dissolved in bottle, start slowly heating.240 DEG C were warming up in 1.5~2 hours；Measure water yield；
Theoretical water yield to be achieved more than 80% when, carry out decompression step by step；Whole reaction, vacuum reaction are finally completed under a high vacuum
About 5~10 hours time.Then with nitrogen pressurising to normal pressure, half an hour is stirred.Finally polyamide is fallen in tetrafluoro plate while hot
On face, particle is cut into after cooling and shaping.
Obtained polyamide hot, after tested, ring and ball softening point are 130 DEG C；Melt viscosity is 6000cp at 200 DEG C.
Preparation example PA II -3
By 0.4mol dimeric dibasic acids (trade mark P1013, big purchased from U.S.'s standing grain), 0.1mol decanedioic acid, 0.2mol ethylenediamines,
In 0.3mol polyetheramine D-230 and 4.5g antioxidant 1010 input 2000ml four-hole boiling flasks, 130 are warming up under nitrogen protection
℃；After component is completely dissolved in bottle, start slowly heating.240 DEG C were warming up in 1.5~2 hours；Measure water yield；Treat
When reaching more than the 80% of theoretical water yield, decompression step by step is carried out；Whole reaction is finally completed under a high vacuum, during vacuum reaction
Between about 5~10 hours.Then with nitrogen pressurising to normal pressure, half an hour is stirred.Finally polyamide is fallen in tetrafluoro plate face while hot
On, particle is cut into after cooling and shaping.
Obtained polyamide hot, after tested, ring and ball softening point are 140 DEG C；Melt viscosity is 8500cp at 200 DEG C.
Comparative example 1
By 0.35mol dimeric dibasic acids (trade mark P1013, big purchased from U.S.'s standing grain), 0.15mol azelaic acids, 0.2mol hexamethylene diamines,
In the input 2000ml four-hole boiling flasks such as 0.15mol piperazines, 0.15mol polyetheramine D-400 and 6.1g antioxidant 1010s, in nitrogen
130 DEG C are warming up under protection；After component is completely dissolved in bottle, start slowly heating.240 DEG C are warming up in 1.5~2h；Meter
Measure water；Theoretical water yield to be achieved more than 80% when, carry out decompression step by step；Finally complete under a high vacuum whole anti-
Should, about 5~10 hours vacuum reaction time.Then with nitrogen pressurising to normal pressure, half an hour is stirred.Finally while hot by polyamide
In in tetrafluoro plate face, particle is cut into after cooling and shaping.
Obtained polyamide hot, after tested, ring and ball softening point are 120 DEG C；Melt viscosity is 5000cp at 200 DEG C.
Embodiment 1
200g, the PA II -1 that preparation example 2 obtains is taken to take 200g, put with 20g polyamide waxes the PA I -1 that preparation example 1 obtains
Enter the BP-8172-A type banburying stoves provided by Dongguan Bao Pin precision instruments Co., Ltd, banburying 20min, takes under the conditions of 130 DEG C
Go out.
Measure 135 DEG C of softening point, 200 DEG C of melt viscosity 10000cp.
Embodiment 2
500g, the PA II -1 that preparation example 2 obtains is taken to take 100g, put with 30g polyamide waxes the PA I -1 that preparation example I is obtained
Enter banburying stove, the banburying 20min under the conditions of 130 DEG C, take out.
Measure 138 DEG C of softening point, 200 DEG C of melt viscosity 9000cp.
Embodiment 3
1 obtained PA I -1, which will be prepared, takes 100g, the PA II -1 that preparation example 2 obtains to take 500g, put with 30g polyamide waxes
Enter banburying stove, the banburying 20min under the conditions of 130 DEG C, take out.
Measure 130 DEG C of softening point, 200 DEG C of melt viscosity 7500cp
Embodiment 4-13
With reference to above-mentioned technique, carry out preparing embodiment 4-13 according to the formula in table 2, formula and performance are shown in Table 2.
The comparative example formula of the present invention of table 1 and performance
Claims (12)
1. a kind of polyamide thermoplastic hot-melt adhesive composition, it is included：
A) the amine type dimeric dibasic acid copolyamide of 5~90 weight % rings two,
B) 5-90 weight % polyether polyamines type dimeric dibasic acid copolyamide, and
C) 1-10 weight % polymer-wax, on the basis of the gross weight of polyamide thermoplastic hot-melt adhesive composition.
2. polyamide thermoplastic hot-melt adhesive composition as claimed in claim 1, it is characterised in that it is included：
A) the amine type dimeric dibasic acid copolyamide of 10~85 weight %5-6 yuan of rings two,
B) 10-85 weight % polyether polyamines type dimeric dibasic acid copolyamide, and
C) 2-8 weight % polymer-wax, on the basis of the gross weight of polyamide thermoplastic hot-melt adhesive composition.
3. polyamide thermoplastic hot-melt adhesive composition as claimed in claim 2, it is characterised in that described 5-6 yuan of rings
Two amine type dimeric dibasic acid copolyamides include：
(1) dicarboxylic acids copolymerization units, it includes：
(a) 70~90 moles of % dimeric dibasic acid copolymerization units, and
(b) 10~30 moles of %C2-C14Aliphatic dicarboxylic acid copolymerization units, using the total mole number of dicarboxylic acids copolymerization units as
Benchmark；And
(2) diamine copolymerization units, it includes：
(c) 50~70 moles of %C2-C8Linear aliphatic diamines unit；With
(d) 30~50 moles of %5-6 yuan of rings diamines units, on the basis of the total mole number of diamine copolymerization units；The 5-6
The number-average molecular weight Mn of the amine type copolyamide of yuan of rings two is 5000~40000.
4. polyamide thermoplastic hot-melt adhesive composition as claimed in claim 1, it is characterised in that described polyether polyamine
Type dimeric dibasic acid copolyamide includes：
(1) dicarboxylic acids copolymerization units, it includes：
(a) 70~90 moles of % dimeric dibasic acid copolymerization units, and
(b) 10~30 moles of %C2-C14Aliphatic dicarboxylic acid copolymerization units, using the total mole number of dicarboxylic acids copolymerization units as
Benchmark；And
(2) diamine copolymerization units, it includes：
(c) 30~50 moles of %C2-C8Linear aliphatic diamines unit；With
(d) 50~70 moles of % polyether polyamine copolymerization units, on the basis of the total mole number of diamine copolymerization units；The polyethers is more
The number-average molecular weight Mn of amine type dimeric dibasic acid copolyamide is 2000~20000.
5. polyamide thermoplastic hot-melt adhesive composition as claimed in claim 3, it is characterised in that described dimeric dibasic acid is
C16~20The dimer of unrighted acid.
6. polyamide thermoplastic hot-melt adhesive composition as claimed in claim 4, it is characterised in that described polyether polyamine
Including the polyethers with 2~3 Amino End Groups, molecular weight is 150~2500.
7. polyamide thermoplastic hot-melt adhesive composition as claimed in claim 6, it is characterised in that described polyether polyamine
Represented with following molecular formula：
Wherein x ≈ 2.5,6.1 or 34,
Or described polyether polyamine is represented with following molecular formula：
8. the polyamide thermoplastic hot-melt adhesive composition as described in claim 3 or 4, it is characterised in that described binary
The ratio between carboxyl acid copolymer unit total mole number and diamine copolymerization units total mole number are 0.95~1.05：0.95~1.05.
9. polyamide thermoplastic hot-melt adhesive composition as claimed in claim 1 or 2, it is characterised in that described polymerization
Thing wax includes polyamide wax, Tissuemat E, acrylate wax or their mixture.
10. polyamide thermoplastic hot-melt adhesive composition as claimed in claim 3, it is characterised in that described 5-6 yuan of rings
Diamines be piperazine, imidazolidine, aminoethyl piperazine, 1,4- bis- (3- aminopropyls) piperazine, cyclohexane diamine, cyclohexyl to dimethylamine,
Different Fu Er ketone diamines, lupetazin, benzene methanediamine, pyridine diamines or their mixture.
11. polyamide thermoplastic hot-melt adhesive composition as claimed in claim 3, it is characterised in that the 5-6 yuan of rings diamines
The number-average molecular weight Mn of type copolyamide is 10000-30000.
12. polyamide thermoplastic hot-melt adhesive composition as claimed in claim 4, it is characterised in that the polyether polyamine type
The number-average molecular weight Mn of dimeric dibasic acid copolyamide is 5000-10000.
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| CN106893094A (en) * | 2017-01-09 | 2017-06-27 | 山东凯恩新材料科技有限公司 | A kind of polyamide hot of uV curable and preparation method thereof |
| CN109868111B (en) * | 2017-12-01 | 2022-06-10 | 上海理日化工新材料有限公司 | Polyamide hot melt adhesive packaging composition |
| EP4136185A4 (en) * | 2020-04-15 | 2024-06-12 | 3M Innovative Properties Company | Branched amorphous polyamide (co)polymers and methods of making and using same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1362461A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Polyamide thermosol |
| CN101861358A (en) * | 2007-11-19 | 2010-10-13 | 纳幕尔杜邦公司 | Use of polyamide compositions for making molded articles having improved adhesion, molded articles thereof and methods for adhering such materials |
| CN103184030A (en) * | 2011-12-28 | 2013-07-03 | 上海轻工业研究所有限公司 | Novel polyamide adhesive |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1362461A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Polyamide thermosol |
| CN101861358A (en) * | 2007-11-19 | 2010-10-13 | 纳幕尔杜邦公司 | Use of polyamide compositions for making molded articles having improved adhesion, molded articles thereof and methods for adhering such materials |
| CN103184030A (en) * | 2011-12-28 | 2013-07-03 | 上海轻工业研究所有限公司 | Novel polyamide adhesive |
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