CN101372610B - Low temperature resistant polyamide thermosol adhesive and use thereof - Google Patents
Low temperature resistant polyamide thermosol adhesive and use thereof Download PDFInfo
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- CN101372610B CN101372610B CN2007100451896A CN200710045189A CN101372610B CN 101372610 B CN101372610 B CN 101372610B CN 2007100451896 A CN2007100451896 A CN 2007100451896A CN 200710045189 A CN200710045189 A CN 200710045189A CN 101372610 B CN101372610 B CN 101372610B
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Abstract
The present invention provides a low-temperature polyamide hot-melt adhesive. The present invention contains unsaturated aliphatic dimer acid polymeric unit and polyamine polymeric unit; wherein, the polyamine polymeric unit contains 50 to 90 mol percent of C2-8 aliphatic diamine polymeric unit and 5 to 50 mol percent of polyether polyamine polymeric unit; the total mol number of polyamine polymeric unit is taken as the benchmark. The polyamide hot-melt adhesive provided by the present invention has excellent low temperature resistance and extensibility, and is especially suitable for automobile industry.
Description
Technical field
The present invention relates to polyamide thermosol adhesive and application thereof, relate more specifically to low temperature resistant polyamide thermosol adhesive and application thereof.
Background technology
The outstanding advantage of polyamide thermosol adhesive is the snappiness that melt temperature is low, melting range is narrow, polarity is strong, bonding strength is high, processing characteristics is good, wear resisting property is good and good, and is usually used in being widely used in the industries such as automobile, electronics, printing packaging and shoes and hats.
Yet polyamide thermosol adhesive has the not high and low shortcoming of unit elongation of resistance to low temperature, is difficult to satisfy some special requirements in the automobile industry.
Summary of the invention
The purpose of this invention is to provide the polyamide thermosol adhesive that a kind of resistance to low temperature and unit elongation all are significantly improved.
Polyamide thermosol adhesive of the present invention comprises unsaturated aliphatic dimeracid polymerized unit and polyamines polymerized unit, and wherein the polyamines polymerized unit contains 50～95 moles of %C
2-8Aliphatie diamine polymerized unit and 5～50 moles of % polyether polyamine polymerized units are benchmark with the total mole number of polyamines polymerized unit.
The present invention also provides the application of above-mentioned polyamide thermosol adhesive in automotive industry.
Description of drawings
Fig. 1 shows a kind of preferred synthetic route of low temperature resistant polyamide thermosol adhesive of the present invention.
Fig. 2 shows the another kind of preferred synthetic route of low temperature resistant polyamide thermosol adhesive of the present invention.
Embodiment
In a preferred implementation, low temperature resistant polyamide thermosol adhesive of the present invention comprises unsaturated aliphatic dimeracid polymerized unit and polyamines polymerized unit, and wherein the polyamines polymerized unit contains 60～90 moles of %C
2-8Aliphatie diamine polymerized unit and 10～40 moles of % polyether polyamine polymerized units are benchmark with the total mole number of polyamines polymerized unit.
In a preferred implementation, the mol ratio of polyamines polymerized unit and unsaturated aliphatic dimeracid polymerized unit is (0.95～1.1): 1, be preferably (0.98～1.05): and 1,1:1 more preferably.
Unsaturated aliphatic dimeracid polymerized unit in the polyamide thermosol adhesive of the present invention is C
16-20The dimeracid polymerized unit of unsaturated fatty acids, for example, by linoleic acid dimer, dimerization oleic acid, dimerization linolenic acid, dimerization elaidic acid, dimerization behenic acid and dimerization eleostearic acid deutero-polymerized unit.C preferably
18The dimeracid polymerized unit of unsaturated fatty acids, for example, by linoleic acid dimer, dimerization oleic acid, dimerization linolenic acid, dimerization elaidic acid, dimerization behenic acid deutero-polymerized unit.
One preferred embodiment in, a part of dimeracid polymerized unit can be by C
6-12The aliphatic dicarboxylic acid unit substitutes, preferably by C
6-10The aliphatic dicarboxylic acid unit substitutes.C
6-12The unitary add-on of aliphatic dicarboxylic acid should be no more than 40% of dimeracid polymerized unit total mole number, preferably is no more than 30%.
Above-mentioned C
6-12The aliphatic dicarboxylic acid unit is by C
6-12The aliphatic dicarboxylic acid derives and obtains.C
6-12The aliphatic dicarboxylic acid for example comprises hexanodioic acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid or its mixture, and preferred example comprises suberic acid, sebacic acid, dodecanedioic acid or its mixture.Preferred example is a sebacic acid.
Aliphatie diamine polymerized unit in the polyamide thermosol adhesive of the present invention is by C
2-8Aliphatie diamine is preferably by C
2-6Aliphatie diamine is derived and is obtained.
The example of above-mentioned aliphatie diamine comprises quadrol, tn, tetramethylenediamine, pentamethylene diamine, 2 methyl pentamethylenediamine, hexanediamine, octamethylenediamine and composition thereof; Preferred example comprises quadrol, tn, tetramethylenediamine, hexanediamine or its mixture, and preferred example is a quadrol.
Polyether polyamine polymerized unit in the polyamide thermosol adhesive of the present invention is derived by polyether polyamine and is obtained.Polyether polyamine comprises having 2-5, preferred 2-3 polyethers that end is amino, and molecular weight is generally 150～2500, is preferably 200～2000.
Polyether polyamine for example comprises polyethyleneoxide diamine, T 46155 triamine, polypropyleneoxide diamine, polyoxypropylene triamine, polyoxy butylene diamines, polyoxy butylene triamine, gathers (1; 2)-the dimethyl oxygen ethylene diamine, gather (1,2)-dimethyl oxygen ethene triamine or their mixture.
Polyether polyamine can make or buy from market by method as known in the art, and D-230 for example can commodity by name, D-400, D-2000 and T-430 buy from BASF AG.
Commodity are called the polyether polyamine of D-230, D-400 and D-2000 and can represent with following molecular formula:
Wherein for D-230, x ≈ 2.5; For D-400, x ≈ 6.1; For D-2000, x ≈ 34.
The polyether polyamine of commodity T-430 by name can be represented with following molecular formula:
Polyamide thermosol adhesive of the present invention is by unsaturated aliphatic dimeracid, C
2-8Aliphatie diamine, polyether polyamine and optional C
6-12Aliphatic dicarboxylic acid's polycondensation makes.This polycondensation usable acid catalysis, for example phosphoric acid or Triple Pressed Stearic Acid catalysis.Sour consumption is 0.01～0.05wt% of total acid monomer weight among the present invention, is preferably 0.015～0.025wt%.
General 120～240 ℃ of the temperature of reaction of above-mentioned polycondensation, reaction between 120～140 ℃ when gradually temperature being risen to 230～240 ℃ then, vacuumizes and carries out polycondensation during beginning.
The preferred polyamide thermosol adhesive of the present invention makes by synthetic route shown in Figure 1.For example, the dimeracid after the weighing is packed in the 1000ml there-necked flask, pour in the constant pressure funnel after the polyetheramine of weighing and quadrol are mixed, wherein the mol ratio of dimeracid and diamines is 1: (0.95～1.10) adds an amount of phosphoric acid and Triple Pressed Stearic Acid; Feed nitrogen, dimeracid is preheating to 130 ℃, drip hybrid diamine gradually, generally in 30 minutes, drip off, the interior temperature of reaction flask is preferably remaining on below 140 ℃ always during dropping, can stop or slowing down rate of addition as surpassing, until all dripping; Slowly promote temperature of reaction by 20 ℃/h heat-up rate,, keep this temperature section 1h at least, and measure distilled water, reach 90% o'clock of theoretical amount, can progressively reduce pressure until being increased to 230～240 ℃; Finally under high vacuum, accomplish entire reaction, make high-molecular weight polymeric amide sample; While hot polymeric amide is fallen on tetrafluoro plate face at last, be cut into particle behind the cooling forming.
The another kind of preferred polyamide thermosol adhesive of the present invention makes by synthetic route shown in Figure 2.Different with synthetic route shown in Figure 1 is in the dimeracid raw material, to add the softening temperature that sebacic acid is adjusted polyamide thermosol adhesive.
The number-average molecular weight Mn of polyamide thermosol adhesive of the present invention is generally 5000～50000, is preferably 10000～40000.
The melt viscosity of polyamide thermosol adhesive of the present invention (200 ℃) is generally 1,000～100, and 000mPa.s is preferably 3,000～80,000mPa.s.
The softening temperature of polyamide thermosol adhesive of the present invention is generally 80～200 ℃, is preferably 100～180 ℃.
Polyamide thermosol adhesive of the present invention has good especially resistance to low temperature, is generally≤-20 ℃, is preferably≤-30 ℃.
Polyamide thermosol adhesive of the present invention also has good especially unit elongation.Unit elongation is generally >=and 450%, be preferably >=500%.
Polyamide thermosol adhesive of the present invention also has high stripping strength and shearing resistance.Polyamide thermosol adhesive of the present invention is specially adapted in the automotive industry.
Embodiment
Following embodiment is used to further specify the present invention, but is to be understood that these embodiment can not be used to limit protection scope of the present invention.
In following embodiment, measure the performance perameter of polyamide thermosol adhesive of the present invention as follows.
The softening temperature test:
On SYP4202-I bituminous softening-point test device, reference standard GB/T15332-94 tests.
The melt viscosity test:
Adopt the melt viscosity of Brookfield DV-E type rotational viscosimeter specimen; Take by weighing the polyamide hot sample of 11.0g; Selecting model during test is the rotor of S27, and temperature is controlled at 160 ℃, and constantly regulates the rotation rotating speed; Make its test value be positioned at 10～90% linearity range, stable back record observed value.
Acid number and amine pH-value determination pH:
A. determination of acid value
Accurately take by weighing 2～5g sample (being accurate to 0.0001g); Place exsiccant 250ml Erlenmeyer flask, add 30ml toluene-alcohol mixed solution, normal temperature or low-grade fever dissolving; With 0.05N Pottasium Hydroxide ethanol standard solution titration to terminal, titration end point is judged by ZDJ-4A type automatical potentiometric titrimeter automatically.Carry out the titration of blank sample simultaneously.
Acid number (mgKOH/g)=56.11 (V
1-V
2) N/W
In the formula: V
1: the sample titration consumes the volume of Pottasium Hydroxide ethanol standardized solution, ml;
V
2: blank titration consumes the volume of Pottasium Hydroxide ethanol standardized solution, ml;
N: the equivalent concentration of Pottasium Hydroxide ethanol standardized solution;
W: example weight, g.
B. amine pH-value determination pH
Accurately take by weighing 0.5g sample (being accurate to 0.0001g), with 30ml chloroform-methanol mixed solution, normal temperature or low-grade fever dissolving, with the titration of 0.05N hydrochloric acid standard solution to terminal, titration end point is judged by ZDJ-4A type automatical potentiometric titrimeter automatically.
Amine value (mgHCL/g)=56.11NV/W
In the formula: N: the equivalent concentration of hydrochloric acid standard solution;
V: the volume of hydrochloric acid standard solution, ml;
W: example weight, g.
Peel strength test:
Place on the thermal-flame calcination to PE material softening fast with wide for the PE material of 25mm; Then the fused polyamide hot is applied on the PE calcination face; With the PE quick-binding that is coated with gluing; Cooling places under the test condition behind the 12h, carries out the stripping strength performance test in model for the GT-AI-3000 tension testing machine.
The shearing resistance test:
With wide be that the aluminium surface treatment of the thick 2mm of 12.5mm is clean, the polymeric amide after melting is applied to the aluminium surface, the overlap joint area is 12.5 * 25 (mm
2), cooling places under the test condition behind the 12h, carries out the shearing resistance performance test in model for the GT-AI-3000 tension testing machine.
The unit elongation test:
By GB sample is processed dumbbell shape, carry out the extension property test for the GT-AI-3000 tension testing machine in model.
The low-temperature performance test:
According to standard A STM-D3111, sample is processed the print of regulation, test through spool test at low temperatures then, thickness of test piece 1.25mm is around shaft diameter 12.8mm.
Comparative Examples 1
In a 1000ml reaction flask that has TM, mechanical stirrer, prolong and a nitrogen access tube, add linoleic acid dimer (available from Shanghai China biochemical worker ltd, trade mark GX92) 335.7 grams, the 36.1g quadrol of packing in the 100ml constant voltage minim pipette feeds nitrogen; Stir, heat temperature raising when 130 ℃ of reaction flask Nei Wenduda, drips quadrol; Temperature is controlled at 130～140 ℃, and after dropping finished, beginning slowly was warming up to about 230 ℃; Temperature-rise period has water to distillate, and when temperature of reaction to 230～240 ℃, carries out decompression vacuum pumping with vacuum pump; Vacuum tightness 100Pa, when power of agitator reached certain value, reaction finished; Remove vacuum, melt is poured on the tetrafluoro plate, obtain yellow adhesive tape (sample 1 in the table 1).
After under 50 ℃ dry 24 hours, 114 ℃ of the softening temperatures that records, melt viscosity 14230mPa.s (200 ℃); Acid number 4.0mgKOH/g, amine value 5.1mgKOH/g records 5 ℃ of resistance to low temperatures; Unit elongation 230%, stripping strength (PE-PE) 150N/25mm, shearing resistance (A1-A1) 7.88N/mm
2
Comparative Examples 2-7
By preparing with Comparative Examples 1 identical mode, different is the quadrol that adopts different proportionings in the system, and quadrol and hexanediamine mixing diamine (sample 2-7 in the table 1).
Embodiment 1
In a 1000ml reaction flask that has TM, mechanical stirrer, prolong and a nitrogen access tube, add linoleic acid dimer (available from Shanghai China biochemical worker ltd, trade mark GX92) 334.8 grams, pack in the 100ml constant voltage minim pipette 21.6g quadrol and 54.7g polyetheramine D-230, feeding nitrogen; Stir, heat temperature raising when 130 ℃ of reaction flask Nei Wenduda, drips mixed amine; Temperature is controlled at 130～140 ℃, and after dropping finished, beginning slowly was warming up to about 230 ℃; Temperature-rise period has water to distillate, and when temperature of reaction to 230～240 ℃, carries out decompression vacuum pumping with vacuum pump; Vacuum tightness 100Pa, when power of agitator reached certain value, reaction finished; Remove vacuum, melt is poured on the tetrafluoro plate, obtain yellow adhesive tape (sample 8 in the table 1).
After under 50 ℃ dry 24 hours, 97 ℃ of the softening temperatures that records, melt viscosity 17950mPa.s (200 ℃); Acid number 3.45mgKOH/g, amine value 0.88mgKOH/g records resistance to low temperature-34 ℃; Unit elongation 450%, stripping strength (PE-PE) 215N/25mm, shearing resistance (A1-A1) 2.75N/mm
2
Embodiment 2-11
By preparing with embodiment 1 identical mode, different is to adopt different polyetheramines in the system, like D-400 and D-2000, and different quadrols and polyetheramine proportioning (sample 9-18 in the table 1).
Embodiment 12
In a 5000ml reaction flask that has TM, mechanical stirrer, prolong and a nitrogen access tube, add linoleic acid dimer (available from Shanghai China biochemical worker ltd, trade mark GX92) 1611 gram and sebacic acid 106g, Triple Pressed Stearic Acid 25g, phosphoric acid 0.36g; Pack in the 1000ml constant voltage minim pipette 143g quadrol and 483 polyetheramine D-400 feed nitrogen, stir heat temperature raising; When 130 ℃ of reaction flask Nei Wenduda, drip mixed amine, temperature is controlled at 130～140 ℃, drip finish after; Beginning slowly is warming up to about 230 ℃, and temperature-rise period has water to distillate, and when temperature of reaction to 230～240 ℃, carries out decompression vacuum pumping with vacuum pump; Vacuum tightness 100Pa, when power of agitator reached certain value, reaction finished; Remove vacuum, melt is poured on the tetrafluoro plate, obtain yellow adhesive tape (sample 19 in the table 1).
After under 50 ℃ dry 24 hours, 145 ℃ of the softening temperatures that records, melt viscosity 4860mPa.s (200 ℃); Acid number 0.79mgKOH/g, amine value 5.57mgKOH/g records resistance to low temperature-22 ℃; Unit elongation 861%, stripping strength (PE-PE) 237N/25mm, shearing resistance (A1-A1) 2.98N/mm
2
Embodiment 13-16
By preparing with embodiment 12 identical modes, different is the sebacic acid (sample 20-23 in the table 1) that adopts different proportionings in the system.
Embodiment 17
By preparing with embodiment 12 identical modes, different is to adopt the different polyetheramines that contain three-functionality-degree in the system, after the discharging; After under 50 ℃ dry 24 hours, 142 ℃ of the softening temperatures that records, melt viscosity 12500mPa.s (200 ℃); Acid number 1.24mgKOH/g, amine value 1.25mgKOH/g records resistance to low temperature-35 ℃; Unit elongation 730%, stripping strength (PE-PE) 210N/25mm, shearing resistance (A1-A1) 2.11N/mm
2(sample 24 in the table 1).
Table 1
Continuous table
Continuous table
Consumption in the table is by mole.
Claims (9)
1. a low temperature resistant polyamide thermosol adhesive is characterized in that it comprises C
16-20Unsaturated aliphatic dimeracid polymerized unit and polyamines polymerized unit, wherein the polyamines polymerized unit contains 50～95 moles of %C
2-8Aliphatie diamine polymerized unit and 5～50 moles of % polyether polyamine polymerized units are benchmark with the total mole number of polyamines polymerized unit, polyamines polymerized unit and C
16-20The mol ratio of unsaturated aliphatic dimeracid polymerized unit is (0.95～1.1): 1, and described polyether polyamine is represented with following molecular formula:
Wherein x ≈ 2.5,6.1 or 34,
Perhaps, described polyether polyamine is represented with following molecular formula:
2. low temperature resistant polyamide thermosol adhesive as claimed in claim 1 is characterized in that, the number-average molecular weight Mn of said polyamide hot is 5000～50000.
3. low temperature resistant polyamide thermosol adhesive as claimed in claim 1 is characterized in that, described polyamines polymerized unit contains 60～90 moles of %C
2-6Aliphatie diamine polymerized unit and 10～40 moles of % polyether polyamine polymerized units are benchmark with the total mole number of polyamines polymerized unit.
4. low temperature resistant polyamide thermosol adhesive as claimed in claim 1 is characterized in that, described unsaturated aliphatic dimeracid is C
18The dimeracid of unsaturated fatty acids.
5. like claim 1 or 3 described low temperature resistant polyamide thermosol adhesives, it is characterized in that described polyether polyamine comprises having 2～3 polyethers that end is amino, molecular weight is 150～2500.
6. low temperature resistant polyamide thermosol adhesive as claimed in claim 5 is characterized in that, the molecular weight of described polyether polyamine is 200～2000.
7. low temperature resistant polyamide thermosol adhesive as claimed in claim 1 is characterized in that it contains C
6-12The aliphatic dicarboxylic acid unit.
8. low temperature resistant polyamide thermosol adhesive as claimed in claim 7 is characterized in that it contains C
6-10The aliphatic dicarboxylic acid unit.
9. the application of low temperature resistant polyamide thermosol adhesive as claimed in claim 1 in automotive industry.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011138459A1 (en) * | 2010-05-07 | 2011-11-10 | Knauf Insulation | Carbohydrate binders and materials made therewith |
| CN101928544B (en) * | 2010-09-21 | 2013-03-13 | 烟台德邦科技有限公司 | Polyamide hot cement with high softening point and low-temperature resistance, and preparing method thereof |
| CN102399364A (en) * | 2011-09-06 | 2012-04-04 | 烟台德邦电子材料有限公司 | Polyamide resin with low softening point and preparation method thereof |
| WO2013062089A1 (en) * | 2011-10-28 | 2013-05-02 | 宇部興産株式会社 | Polyamide resin and molded article formed therefrom |
| CN102492135A (en) * | 2011-11-30 | 2012-06-13 | 上海天洋热熔胶有限公司 | Method for synthesizing dimer acid type polyamide hot melt adhesive |
| CN103184030B (en) * | 2011-12-28 | 2014-11-12 | 上海轻工业研究所有限公司 | Novel polyamide adhesive |
| CN102703021A (en) * | 2012-06-07 | 2012-10-03 | 昆山天洋热熔胶有限公司 | High-air permeability dimer acid type polyamide hot melt adhesive and preparation method thereof |
| CN109605878A (en) * | 2018-12-17 | 2019-04-12 | 吕拴力 | A kind of fabrication polyamide adhesive material |
| CN111040721B (en) * | 2019-12-02 | 2023-03-17 | 天洋新材(上海)科技股份有限公司 | Low-VOC copolyamide hot melt adhesive and preparation method thereof |
| CN114395363A (en) * | 2022-01-24 | 2022-04-26 | 四川大学 | Polyamide hot melt adhesive and preparation method and application thereof |
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Application publication date: 20090225 Assignee: Liri Chemical New Materials Co., Ltd. Shanghai Assignor: Shanghai Light Industry Research Institute Co., Ltd. Contract record no.: 2013310000070 Denomination of invention: Low temperature resistant polyamide thermosol adhesive and use thereof Granted publication date: 20120523 License type: Exclusive License Record date: 20130705 |
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Effective date of registration: 20170605 Address after: 200031 Shanghai City Baoqing Road No. 20 Co-patentee after: Liri Chemical New Materials Co., Ltd. Shanghai Patentee after: Shanghai Light Industry Research Institute Co., Ltd. Address before: 200031 Shanghai City Baoqing Road No. 20 Patentee before: Shanghai Light Industry Research Institute Co., Ltd. |