CN104673177A - Thermoplastic polyamide hot-melt adhesive composition - Google Patents
Thermoplastic polyamide hot-melt adhesive composition Download PDFInfo
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- CN104673177A CN104673177A CN201310630079.1A CN201310630079A CN104673177A CN 104673177 A CN104673177 A CN 104673177A CN 201310630079 A CN201310630079 A CN 201310630079A CN 104673177 A CN104673177 A CN 104673177A
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Abstract
The invention relates to a thermoplastic polyamide hot-melt adhesive composition. The thermoplastic polyamide hot-melt adhesive composition comprises the following components in percentage by weight based on the total weight of the composition: (a) 5-90 percent of cyclo-diamine type copolyamide; (b) 5-90 percent of polyoxypropylene polyamine type copolyamide; and (c) 1-10 percent of polymer wax. The hot-melt adhesive composition disclosed by the invention has excellent adhesive property on metal aluminum and ray-crosslinked polyethylene plates and is short in opening time and high in curing speed, and the production efficiency is improved.
Description
Technical field
The present invention relates to polyamide thermoplastic hot-melt adhesive composition, particularly relate to the plastic polyamide hot-melt adhesive composition to having superior adhesion energy to metallic aluminium and radiant crosslinked polyethylene plate.
Background technology
Polymeric amide as tackiness agent mainly contains two classes, and what molecular weight was higher is copolyamide, and this kind of polyamide hot has excellent water-fastness and dry cleaning resistance energy, is widely used in the bonding of fiber, very large at textile industry consumption.Another kind of polymeric amide is formed by dimeracid and diamine polycondensation, has the advantages such as melting range is narrow, quick solidifying, adhesiveproperties are excellent, be widely used in the fields such as shoemaking, automobile, electronics, material contracting with heat at present.
Research both at home and abroad for polyamide adhesives has had a lot, especially to the improvement of dimer acid type polyamide, by adopting the mode of blended or copolymerization, improves shortcomings such as its fragility, the easily moisture absorption.In US4670552 patent, by polymeric amide and polyesteramide blended, obtain one and there is the flexible hot melt adhesive of high and low temperature, have materials such as polyethylene, polyester, polymeric amide and PVC good bonding; US5989385, by blended to dimeric acid type polyamide hot melt adhesive and Gum Rosin, terpine resin, EVA etc., obtain a kind of hot melt adhesive, is applied in bookbinding aspect, can carry out bookbinding at relatively low temperature.In recent years, the domestic research for dimer acid type polyamide also result in the attention of insider.CN101372610 is by introducing the oligopolymer modification such as polyethylene oxide diamine or propylene oxide diamines, and compare traditional dimer acid type polyamide, its toughness is greatly improved, and low temperature resistantly reaches less than-40 DEG C; CN101633829, by introducing active paracril, improves the stopping property of polyamide adhesives, makes it to be widely used in heat-shrinkable T bush.
Dimeric acid type polyamide hot melt adhesive is due to the performance of excellence, and Application Areas is in continuous expansion.But single use dimer acid type polyamide is as sizing agent, in the occasion of some particular requirement, still there are some defects in performance, especially under some dynamic working conditionss, as under high and low temperature alternative conversion condition, toughness, adhesiveproperties and sealing property will maintain a good state lastingly, and this is difficult to accomplish for single dimer acid type polyamide.So need the performance of comprehensive different copolymer acid amides, to reach the high sizing agent of comprehensive use properties.
Therefore, good in the urgent need to a kind of adhesiveproperties in this area, simultaneously the open hour shorter, quick solidifying and the high polyamide binder of production efficiency.
Summary of the invention
The present invention passes through two kinds of copolyamide melt blendings, obtain a kind of polymeric amide Adhesive composition, combine the advantage of the polymeric amide sizing agent that different copolymer monomer obtains, avoid open hour of too much bringing due to comonomer in single copolyamide long shortcoming simultaneously.
Therefore, the invention provides a kind of polyamide thermoplastic hot-melt adhesive composition, it comprises:
A) 5 ~ 90 % by weight ring two amine type dimeracid copolyamides,
B) 5-90 % by weight polyether polyamine type dimeracid copolyamide, and
C) 1-10 % by weight polymer-wax, with the gross weight of polyamide thermoplastic hot-melt adhesive composition for benchmark.
Compare the dimer acid type polyamide sizing agent be used alone, this polyamide thermosol composition has and greatly improves non-polar material and the bonding of polar material, to the polyethylene base material of heat-shrinkable T bush, there is good stopping property, water-intake rate is extremely low, ageing-resistant performance is excellent, can be applicable to the occasion of temperature checker, service requirements harshness.Compare single copolyamide, set time is short, saves the applying glue time.Be easy to suitability for industrialized production.
Embodiment
In one preferred embodiment, the invention provides a kind of polyamide thermoplastic hot-melt adhesive composition, it comprises:
A) 10 ~ 85 % by weight 5-6 ring two amine type dimeracid copolyamides,
B) 10-85 % by weight polyether polyamine type dimeracid copolyamide, and
C) 2-8 % by weight polymer-wax, with the gross weight of polyamide thermoplastic hot-melt adhesive composition for benchmark.
In a preferred embodiment, above-mentioned 5-6 ring two amine type dimeracid copolyamide comprises:
(1) di-carboxylic acid copolymerization units, it comprises:
(a) 70 ~ 90 % by mole of dimeracid copolymerization units, and
(b) 10 ~ 30 % by mole of C
2-C
14aliphatic dicarboxylic acid copolymerization units, with the total mole number of di-carboxylic acid copolymerization units for benchmark; And
(2) diamine copolymerization units, it comprises:
(c) 50 ~ 70 % by mole of C
2-C
8linear aliphatic diamines unit; With
D () 30 ~ 50 % by mole of 5-6 ring diamines unit, with the total mole number of diamine copolymerization units for benchmark; The number-average molecular weight Mn of this 5-6 ring two amine type dimeracid copolyamide is 5000 ~ 40000; Be preferably 10000-30000.
In a preferred embodiment, above-mentioned polyether polyamine type dimeracid copolyamide comprises:
(1) di-carboxylic acid copolymerization units, it comprises:
(a) 70 ~ 90 % by mole of dimeracid copolymerization units, and
(b) 10 ~ 30 % by mole of C
2-C
14aliphatic dicarboxylic acid copolymerization units, with the total mole number of di-carboxylic acid copolymerization units for benchmark; And
(2) diamine copolymerization units, it comprises:
(c) 30 ~ 50 % by mole of C
2-C
8linear aliphatic diamines unit; With
D () 50 ~ 70 % by mole of polyether polyamine copolymerization units, with the total mole number of diamine copolymerization units for benchmark; The number-average molecular weight Mn of this polyether polyamine type dimeracid copolyamide is 2000 ~ 20000; Be preferably 5000-10000.
Polyamide thermoplastic hot melt adhesive composition of the present invention is obtained by 5-6 ring two amine type dimeracid copolyamide PA I and other auxiliary agent melt blendings such as polyether polyamine type dimeracid copolyamide PA II and polymer-wax.
Above-mentioned 5-6 ring two amine type dimeracid copolyamide component PA I is by dimeracid and optional C
6-C
14aliphatic dicarboxylic acid and C
2-C
8the comonomer copolycondensations such as straight-chain aliphatic diamines and 5-6 ring diamines obtain.
Above-mentioned polyether polyamine type dimeracid copolyamide PA II is by dimeracid and optional C
6-C
14aliphatic dicarboxylic acid and C
2-C
8the comonomer copolycondensations such as straight-chain aliphatic diamines and polyether polyamine obtain.
Dimeracid copolymerization units contained in above-mentioned 5-6 ring two amine type copolyamide PA I and polyether polyamine type copolyamide PA II is by C
16~
20the dimer of unsaturated fatty acids derives and obtains.Above-mentioned dimeracid is such as by the derivative dimeracid of linolic acid, oleic acid, linolenic acid, elaidic acid, behenic acid, eleostearic acid or appropriate youngster oil.Preferably C
18the dimeracid of unsaturated fatty acids, such as, the dimeracid obtained by dimerization such as appropriate youngster's oil, linolic acid, oleic acid or linolenic acid.Dimeracid such as comprises linoleic acid dimer, dimerization oleic acid, dimerization linolenic acid, dimerization elaidic acid, dimerization behenic acid, dimerization eleostearic acid or their mixture.
Dimer acid material for the preparation of 5-6 ring two amine type copolyamide PA I and polyether polyamine type copolyamide PA II requires that dimeracid content is at more than 65wt%, preferably 75 ~ 95wt%, and preferred dimerization component concentration is at 90 ~ 97wt%; Three acid contents at below 15wt%, preferably 3 ~ 10wt%; Single below acid content 5wt%, preferred content is at 1 ~ 3wt%.Dimeracid can buied on the market.
Above-mentioned 5-6 ring two amine type dimeracid copolyamide the PA I and C contained by polyether polyamine type dimeracid copolyamide PA II
2-C
14aliphatic dicarboxylic acid copolymerization units is C
2-C
14aliphatic dicarboxylic acid derives.Preferred aliphatic dicarboxylic acid is C
4-C
12straight-chain aliphatic di-carboxylic acid, is more preferably C
6-C
10straight-chain aliphatic di-carboxylic acid.Above-mentioned aliphatic dicarboxylic acid such as comprises oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, DC11, ten binary diprotic acid, ten ternary diprotic acid, 15 yuan of di-carboxylic acid, ten hexa-atomic di-carboxylic acid or their mixtures.Preferred example is nonane diacid, sebacic acid or their mixture.
Above-mentioned 5-6 ring two amine type dimeracid copolyamide the PA I and C contained by polyether polyamine type dimeracid copolyamide PA II
2-C
8linear aliphatic diamines unit is by C
2-C
8aliphatic series diamine derives.Above-mentioned aliphatic diamine such as comprises quadrol, propylene diamine, butanediamine, hexanediamine, heptamethylene diamine, pentamethylene diamine, 2 methyl pentamethylenediamine, octamethylenediamine or their mixture.Preferred aliphatic diamine such as comprises quadrol, propylene diamine, butanediamine, hexanediamine or its mixture, and preferred aliphatic diamine such as comprises quadrol, hexanediamine or its mixture.
Ring diamines unit contained by above-mentioned 5-6 ring two amine type dimeracid copolyamide PA I is derived by ring diamines.Described ring diamines comprises alicyclic diamine, aromatic ring diamines, heterocyclic diamine or their mixture.Preferred ring diamines is the ring diamines containing 5-6 unit alicyclic ring, aromatic ring or nitrogen heterocyclic.The nitrogen-atoms of the amine formed can be included in ring, also can be positioned on ring outside chain.Above-mentioned ring diamines such as comprises piperazine, tetrahydroglyoxaline, aminoethyl piperazine, 1,4-bis-(3-aminopropyl) piperazine, cyclohexane diamine, cyclohexyl are to dimethylamine, different Fu Er ketone diamines, lupetazin, benzene methanediamine, pyridine diamines etc., wherein a kind of or its mixture, be preferably cyclohexyl diamine, lupetazin, piperazine etc., be more preferably piperazine.
Polyether polyamine copolymerization units contained by above-mentioned polyether polyamine type dimeracid copolyamide PA II is derived by polyether polyamine and obtains.Above-mentioned polyether polyamine comprises and has 2-5, the polyethers of a preferred 2-3 Amino End Group, and molecular weight is generally 150 ~ 4000, and preferably 200 ~ 2000.
Above-mentioned polyether polyamine such as comprises polyethyleneoxide diamine, polyoxyethylene triamine, polypropyleneoxide diamine, polyoxypropylene triamine, polybutylene diamines, polybutylene triamine, poly-(1,2)-dimethyl oxygen ethylene diamine, poly-(1,2)-dimethyl oxygen ethene triamine or their mixture, the preferred trade mark has the one in polyetheramine D-230, polyetheramine D-400, polyetheramine D-2000 or polyetheramine T-403 or any several mixture.
The polyether polyamine that commodity are called D-230, D-400 and D-2000 can represent by following molecular formula:
Wherein for D-230, x ≈ 2.5; For D-400, x ≈ 6.1; For D-2000, x ≈ 34.
The polyether polyamine that commodity are called T-430 can represent by following molecular formula:
General 120 ~ 240 DEG C of the temperature of reaction of above-mentioned copolycondensation, reacts during beginning, when then gradually temperature being risen to 230 ~ 240 DEG C, vacuumizes and carry out polycondensation between 120 ~ 140 DEG C.
In a particularly preferred embodiment, above-mentioned 5-6 ring two amine type dimeracid copolyamide PAI such as obtains as follows: by dimeracid, C after weighing
2-C
14aliphatic dicarboxylic acid, C
2-C
8linear aliphatic diamines, ring diamines and a small amount of oxidation inhibitor etc. load in 2000ml four-hole boiling flask, wherein total mol ratio of dimeracid and diamines is 1:(0.95 ~ 1.10), nitrogen is passed in four-hole boiling flask, by heating temperatures in this reaction flask to 120-140 DEG C, make various raw materials melt mixing in reaction flask, slowly temperature of reaction is promoted by 20 DEG C/h of heat-up rates, until be increased to 230 ~ 240 DEG C, keep this temperature section at least 1 hour, and measure the water distillated, when reaching 80% of theoretical amount, decompression step by step can be carried out; Finally complete whole reaction under a high vacuum, the polyamide sample of obtained high molecular; Finally while hot polymeric amide is fallen on tetrafluoro plate face, after cooling forming, be cut into particle.
In another particularly preferred embodiment, above-mentioned polyether polyamine type dimeracid copolyamide PAII such as obtains as follows: by dimeracid, C after weighing
2-C
14aliphatic dicarboxylic acid, C
2-C
8linear aliphatic diamines, polyether polyamine and a small amount of oxidation inhibitor etc. load in 2000ml four-hole boiling flask, wherein the mol ratio of dimeracid and diamines is 1:(0.95 ~ 1.10), nitrogen is passed in four-hole boiling flask, by heating temperatures in this reaction flask to 120-140 DEG C, make various raw materials melt mixing in reaction flask, slowly temperature of reaction is promoted by 20 DEG C/h of heat-up rates, until be increased to 230 ~ 240 DEG C, keep this temperature section at least 1 hour, and measure the water distillated, when reaching 80% of theoretical amount, decompression step by step can be carried out; Finally complete whole reaction under a high vacuum, the polyamide sample of obtained high molecular; Finally while hot polymeric amide is fallen on tetrafluoro plate face, after cooling forming, be cut into particle.
Then, above-mentioned obtained 5-6 ring two amine type dimeracid copolyamide PAI, polyether polyamine type dimeracid copolyamide PAII and polymer-wax are weighed, put into a twin screw or Banbury mixer banburying 10-30 minute at 120-140 DEG C, obtain polyamide thermoplastic hot-melt adhesive composition of the present invention.
Polymer-wax contained in polyamide thermoplastic hot-melt adhesive composition of the present invention comprises polyamide wax, polyethylene wax, vinylformic acid ester type waxes or their mixture.The number-average molecular weight of polymer-wax at 1000-5000, preferred 2000-4000.
The softening temperature of polyamide thermoplastic hot-melt adhesive composition of the present invention can adjust in wider scope, and suitability is wide, and viscosity is low, is easy to processing; And excellent to the adhesiveproperties of metal and difficult viscous plastic, the open hour are short, quick solidifying.Can be applicable to various bonding field.
Oxidation inhibitor, anti ultraviolet agent, nucleator, impact modifier, lubricant etc. conventional in this area can also be added on a small quantity in polyamide thermoplastic hot-melt adhesive composition of the present invention.
Contriver also finds in further application test, compare and be used alone dimer acid polyamide hotmelt, polyamide thermoplastic hot-melt adhesive composition of the present invention effectively improves set time, other performances also have synergy simultaneously, and adhesiveproperties and mobility all increase than single polyamide hot.And each component compatibility in composition is good, there is no the phenomenon of phase-splitting.
Polyamide thermoplastic hot-melt adhesive composition softening point range of the present invention is at 110 DEG C ~ 180 DEG C, and melt viscosity when 200 DEG C, at 2000 ~ 15000cp, is preferably 5000-12000cp.Through to metal A l and radiant crosslinked polyethylene board test, there is excellent adhesiveproperties.Open hour are shorter simultaneously, and quick solidifying, improves production efficiency.
Embodiment
Following embodiment is used for further illustrating the present invention, but is to be understood that these embodiments can not be used for limiting the scope of the invention.
In the following example, the performance perameter of polyamide thermosol adhesive of the present invention is measured as follows.
Softening temperature is tested: test by standard GB/T15332-94.
Melt viscosity is tested: adopt Brookfield DV-E type rotational viscosimeter test sample at the melt viscosity of 232 DEG C.
Open hour test: test according to standard HG/T3716-2003.
Bonding strength is tested:
Bonding to PE of PE: the wide PE material for 25mm to be placed on thermal-flame quick calcination to PE material softening, then the polyamide hot of melting is applied on PE calcination face, the PE quick-binding of gluing will be coated with, cooling, being placed under test condition after 12h, is that GT-AI-3000 tension testing machine carries out stripping strength performance test in model.
Bonding to Al of Al: by wide for length be 100mm, wide 25mm, thickness is the aluminium flake surface acetone wiped clean of 1mm, then the polyamide hot of melting is applied on surface-treated aluminium flake, another sheet aluminium flake quick-binding, cooling, under being placed in 10 kgf pressure, room temperature is that GT-AI-3000 tension testing machine carries out stripping strength performance test in model after placing 12h.
Preparation example PA I-1
By 0.4mol dimeracid (trade mark is P1013, and purchased from American standing grain is large), 0.1mol nonane diacid, 0.3mol hexanediamine, 0.2mol piperazine and a small amount of 5.2g antioxidant 1010 drop in 2000ml four-hole boiling flask, are warming up to 130 DEG C under nitrogen protection; After in bottle, component is dissolved completely, start slowly to heat up.240 DEG C are warming up in 1.5 ~ 2 hours; Measure the water yield; Theoretical aquifer yield to be achieved more than 80% time, carry out decompression step by step; Finally complete whole reaction under a high vacuum, about 5 ~ 10 hours vacuum reaction time.Then use nitrogen pressurising under normal pressure, stir half an hour.Finally while hot polymeric amide is fallen on tetrafluoro plate face, after cooling forming, be cut into particle.
The polyamide hot obtained, after tested, ring and ball softening point is 140 DEG C; When 200 DEG C, melt viscosity is 12000cp.
Preparation example PA I-2
By 0.4mol dimeracid (trade mark is P1013, and purchased from American standing grain is large), 0.1mol nonane diacid, 0.3mol quadrol, 0.2mol aminoethyl piperazine and a small amount of 5.4g antioxidant 1010 drop in 2000ml four-hole boiling flask, are warming up to 130 DEG C under nitrogen protection; After in bottle, component is dissolved completely, start slowly to heat up.240 DEG C are warming up in 1.5 ~ 2 hours; Measure the water yield; Theoretical aquifer yield to be achieved more than 80% time, carry out decompression step by step; Finally complete whole reaction under a high vacuum, about 5 ~ 10 hours vacuum reaction time.Then use nitrogen pressurising under normal pressure, stir half an hour.Finally while hot polymeric amide is fallen on tetrafluoro plate face, after cooling forming, be cut into particle.
The polyamide hot obtained, after tested, ring and ball softening point is 135 DEG C; When 200 DEG C, melt viscosity is 11000cp.
Preparation example PA I-3
By 0.4mol dimeracid, (trade mark is P1013, purchased from American standing grain is large), 0.1mol nonane diacid, 0.3mol quadrol, 0.2mol1,4-bis-(3-aminopropyl) piperazine and a small amount of 5.5g antioxidant 1010 drop in 2000ml four-hole boiling flask, are warming up to 130 DEG C under nitrogen protection; After in bottle, component is dissolved completely, start slowly to heat up.240 DEG C are warming up in 1.5 ~ 2 hours; Measure the water yield; Theoretical aquifer yield to be achieved more than 80% time, carry out decompression step by step; Finally complete whole reaction under a high vacuum, about 5 ~ 10 hours vacuum reaction time.Then use nitrogen pressurising under normal pressure, stir half an hour.Finally while hot polymeric amide is fallen on tetrafluoro plate face, after cooling forming, be cut into particle.
The polyamide hot obtained, after tested, ring and ball softening point is 130 DEG C; When 200 DEG C, melt viscosity is 9500cp.
Preparation example PA I-4
By 0.4mol dimeracid (trade mark is P1013, and purchased from American standing grain is large), 0.1mol nonane diacid, 0.3mol quadrol, 0.2mol drop in 2000ml four-hole boiling flask benzene methanediamine and 5.5g antioxidant 1010, are warming up to 130 DEG C under nitrogen protection; After in bottle, component is dissolved completely, start slowly to heat up.240 DEG C are warming up in 1.5 ~ 2 hours; Measure the water yield; Theoretical aquifer yield to be achieved more than 80% time, carry out decompression step by step; Finally complete whole reaction under a high vacuum, about 5 ~ 10 hours vacuum reaction time.Then use nitrogen pressurising under normal pressure, stir half an hour.Finally while hot polymeric amide is fallen on tetrafluoro plate face, after cooling forming, be cut into particle.
The polyamide hot obtained, after tested, ring and ball softening point is 145 DEG C; When 200 DEG C, melt viscosity is 7500cp.
Preparation example PA II-1
By 0.4mol dimeracid (trade mark is P1013, and purchased from American standing grain is large), 0.1mol sebacic acid, 0.2mol quadrol, 0.3mol polyetheramine D-400 and 5.5g antioxidant 1010 drop in 2000ml four-hole boiling flask, are warming up to 130 DEG C under nitrogen protection; After in bottle, component is dissolved completely, start slowly to heat up.240 DEG C are warming up in 1.5 ~ 2 hours; Measure the water yield; Theoretical aquifer yield to be achieved more than 80% time, carry out decompression step by step; Finally complete whole reaction under a high vacuum, about 5 ~ 10 hours vacuum reaction time.Then use nitrogen pressurising under normal pressure, stir half an hour.Finally while hot polymeric amide is fallen on tetrafluoro plate face, after cooling forming, be cut into particle.
The polyamide hot obtained, after tested, ring and ball softening point is 135 DEG C; When 200 DEG C, melt viscosity is 7000cp.
Preparation example PA II-2
By 0.4mol dimeracid (trade mark is P1013, and purchased from American standing grain is large), 0.1mol sebacic acid, 0.4mol quadrol, 0.1mol polyetheramine D-2000 and 6.6g antioxidant 1010 drop in 2000ml four-hole boiling flask, are warming up to 130 DEG C under nitrogen protection; After in bottle, component is dissolved completely, start slowly to heat up.240 DEG C are warming up in 1.5 ~ 2 hours; Measure the water yield; Theoretical aquifer yield to be achieved more than 80% time, carry out decompression step by step; Finally complete whole reaction under a high vacuum, about 5 ~ 10 hours vacuum reaction time.Then use nitrogen pressurising under normal pressure, stir half an hour.Finally while hot polymeric amide is fallen on tetrafluoro plate face, after cooling forming, be cut into particle.
The polyamide hot obtained, after tested, ring and ball softening point is 130 DEG C; When 200 DEG C, melt viscosity is 6000cp.
Preparation example PA II-3
By 0.4mol dimeracid (trade mark is P1013, and purchased from American standing grain is large), 0.1mol sebacic acid, 0.2mol quadrol, 0.3mol polyetheramine D-230 and 4.5g antioxidant 1010 drop in 2000ml four-hole boiling flask, are warming up to 130 DEG C under nitrogen protection; After in bottle, component is dissolved completely, start slowly to heat up.240 DEG C are warming up in 1.5 ~ 2 hours; Measure the water yield; Theoretical aquifer yield to be achieved more than 80% time, carry out decompression step by step; Finally complete whole reaction under a high vacuum, about 5 ~ 10 hours vacuum reaction time.Then use nitrogen pressurising under normal pressure, stir half an hour.Finally while hot polymeric amide is fallen on tetrafluoro plate face, after cooling forming, be cut into particle.
The polyamide hot obtained, after tested, ring and ball softening point is 140 DEG C; When 200 DEG C, melt viscosity is 8500cp.
Comparative example 1
By 0.35mol dimeracid, (trade mark is P1013, purchased from American standing grain is large), 0.15mol nonane diacid, 0.2mol hexanediamine, 0.15mol piperazine, 0.15mol polyetheramine D-400 and 6.1g antioxidant 1010 etc. drop in 2000ml four-hole boiling flask, are warming up to 130 DEG C under nitrogen protection; After in bottle, component is dissolved completely, start slowly to heat up.240 DEG C are warming up in 1.5 ~ 2h; Measure the water yield; Theoretical aquifer yield to be achieved more than 80% time, carry out decompression step by step; Finally complete whole reaction under a high vacuum, about 5 ~ 10 hours vacuum reaction time.Then use nitrogen pressurising under normal pressure, stir half an hour.Finally while hot polymeric amide is fallen on tetrafluoro plate face, after cooling forming, be cut into particle.
The polyamide hot obtained, after tested, ring and ball softening point is 120 DEG C; When 200 DEG C, melt viscosity is 5000cp.
Embodiment 1
The PA I-1 preparation example 1 obtained gets 200g, and the PA II-1 that preparation example 2 obtains gets 200g, puts into the BP-8172-A type banburying stove provided by Dongguan Bao Pin precision instrument company limited, banburying 20min under 130 DEG C of conditions with 20g polyamide wax, takes out.
Record softening temperature 135 DEG C, 200 DEG C of melt viscosity 10000cp.
Embodiment 2
The PA I-1 obtained by preparation example I gets 500g, and the PA II-1 that preparation example 2 obtains gets 100g, puts into banburying stove with 30g polyamide wax, banburying 20min under 130 DEG C of conditions, takes out.
Record softening temperature 138 DEG C, 200 DEG C of melt viscosity 9000cp.
Embodiment 3
The PA I-1 preparation 1 example obtained gets 100g, and the PA II-1 that preparation example 2 obtains gets 500g, puts into banburying stove with 30g polyamide wax, banburying 20min under 130 DEG C of conditions, takes out.
Record softening temperature 130 DEG C, 200 DEG C of melt viscosity 7500cp
Embodiment 4-13
With reference to above-mentioned technique, be prepared embodiment 4-13 according to the formula in table 2, formula and performance are in table 2.
Table 1 comparative example formula of the present invention and performance
Claims (10)
1. a polyamide thermoplastic hot-melt adhesive composition, it comprises:
A) 5 ~ 90 % by weight ring two amine type dimeracid copolyamides,
B) 5-90 % by weight polyether polyamine type dimeracid copolyamide, and
C) 1-10 % by weight polymer-wax, with the gross weight of polyamide thermoplastic hot-melt adhesive composition for benchmark.
2. polyamide thermoplastic hot-melt adhesive composition as claimed in claim 1, it is characterized in that, it comprises:
A) 10 ~ 85 % by weight 5-6 ring two amine type dimeracid copolyamides,
B) 10-85 % by weight polyether polyamine type dimeracid copolyamide, and
C) 2-8 % by weight polymer-wax, with the gross weight of polyamide thermoplastic hot-melt adhesive composition for benchmark.
3. polyamide thermoplastic hot-melt adhesive composition as claimed in claim 1 or 2, it is characterized in that, described 5-6 ring two amine type dimeracid copolyamide comprises:
(1) di-carboxylic acid copolymerization units, it comprises:
(a) 70 ~ 90 % by mole of dimeracid copolymerization units, and
(b) 10 ~ 30 % by mole of C
2-C
14aliphatic dicarboxylic acid copolymerization units, with the total mole number of di-carboxylic acid copolymerization units for benchmark; And
(2) diamine copolymerization units, it comprises:
(c) 50 ~ 70 % by mole of C
2-C
8linear aliphatic diamines unit; With
D () 30 ~ 50 % by mole of 5-6 ring diamines unit, with the total mole number of diamine copolymerization units for benchmark; The number-average molecular weight Mn of this 5-6 ring two amine type copolyamide is 5000 ~ 40000; Be preferably 10000-30000.
4. polyamide thermoplastic hot-melt adhesive composition as claimed in claim 1 or 2, it is characterized in that, described polyether polyamine type dimeracid copolyamide comprises:
(1) di-carboxylic acid copolymerization units, it comprises:
(a) 70 ~ 90 % by mole of dimeracid copolymerization units, and
(b) 10 ~ 30 % by mole of C
2-C
14aliphatic dicarboxylic acid copolymerization units, with the total mole number of di-carboxylic acid copolymerization units for benchmark; And
(2) diamine copolymerization units, it comprises:
(c) 30 ~ 50 % by mole of C
2-C
8linear aliphatic diamines unit; With
D () 50 ~ 70 % by mole of polyether polyamine copolymerization units, with the total mole number of diamine copolymerization units for benchmark; The number-average molecular weight Mn of this polyether polyamine type dimeracid copolyamide is 2000 ~ 20000; Be preferably 5000-10000.
5. the polyamide thermoplastic hot-melt adhesive composition as described in claim 3 or 4, is characterized in that, described dimeracid is C
16~
20the dimer of unsaturated fatty acids.
6. the polyamide thermoplastic hot-melt adhesive composition as described in claim 3 or 4, is characterized in that, described polyether polyamine comprises the polyethers with 2 ~ 3 Amino End Group, and molecular weight is 150 ~ 2500.
7. polyamide thermoplastic hot-melt adhesive composition as claimed in claim 6, is characterized in that, representing by following molecular formula of described polyether polyamine:
Wherein x ≈ 2.5,6.1 or 34,
Or the following molecular formula of described polyether polyamine represents:
8. polyamide thermoplastic hot-melt adhesive composition as claimed in claim 1 or 2, it is characterized in that, described di-carboxylic acid copolymerization units total mole number is 0.95 ~ 1.05:0.95 ~ 1.05 with the ratio of diamine copolymerization units total mole number.
9. polyamide thermoplastic hot-melt adhesive composition as claimed in claim 1 or 2, it is characterized in that, described polymer-wax comprises polyamide wax, polyethylene wax, vinylformic acid ester type waxes or their mixture.
10. polyamide thermoplastic hot-melt adhesive composition as claimed in claim 3, it is characterized in that, described 5-6 ring diamines is that piperazine, imidazolidine, aminoethyl piperazine, Isosorbide-5-Nitrae-two (3-aminopropyl) piperazine, cyclohexane diamine, cyclohexyl are to dimethylamine, different Fu Er ketone diamines, lupetazin, benzene methanediamine, pyridine diamines or their mixture.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN109868111A (en) * | 2017-12-01 | 2019-06-11 | 上海理日化工新材料有限公司 | A kind of polyamide hot encapsulating composition |
| CN115427532A (en) * | 2020-04-15 | 2022-12-02 | 3M创新有限公司 | Branched amorphous polyamide (co) polymers and methods of making and using the same |
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| 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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| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN109868111A (en) * | 2017-12-01 | 2019-06-11 | 上海理日化工新材料有限公司 | A kind of polyamide hot encapsulating composition |
| 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 |
| CN115427532A (en) * | 2020-04-15 | 2022-12-02 | 3M创新有限公司 | Branched amorphous polyamide (co) polymers and methods of making and using the same |
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|---|---|
| CN104673177B (en) | 2017-11-14 |
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