CN104592930B - Hot melt adhesive with compression sensitivity and preparation method thereof - Google Patents
Hot melt adhesive with compression sensitivity and preparation method thereof Download PDFInfo
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- CN104592930B CN104592930B CN201510011375.2A CN201510011375A CN104592930B CN 104592930 B CN104592930 B CN 104592930B CN 201510011375 A CN201510011375 A CN 201510011375A CN 104592930 B CN104592930 B CN 104592930B
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Abstract
The invention relates to a hot melt adhesive with compression sensitivity. The high-temperature melt viscosity at the temperature of 150 DEG C is 1500-15000mPa.s, the Shore hardness is 10-40, the tensile strength is 0.1-1MPa, and the elongation at break is more than 1000 percent. The hot melt adhesive is characterized by comprising the following components in percentage by mole through condensation polymerization: 30-45 percent of dimer acids, 5-20 percent of aliphatic dicarboxylic acids, 20-30 percent of aliphatic diamine, 15-25 percent of polyether amine, 0.01-0.06 percent of an end-capping reagent and 0.01-0.1 percent of an acid catalyst, wherein the mole number of the aliphatic dicarboxylic acids is less than or equal to 40 percent of the mole number of the dimer acids. The hot melt adhesive disclosed by the invention has the beneficial effects that the hot melt adhesive with compression sensitivity has high high-temperature melt viscosity, high toughness and high base material adhesion force and is applied to pressure sensitive adhesive tapes and glue in the manufacturing industry.
Description
Technical field
The present invention relates to a kind of PUR and preparation method thereof, particularly to a kind of polyamide hot with pressure-sensitive
And preparation method thereof, belong to adhesive area.
Background technology
Polyamide hot is typically formed by dimeric dibasic acid, aliphatic dibasic acid and diamine or polyamine polycondensation, has molten
Point range is narrow, softening point is high, nontoxic, oil resistant chemical resistance is good, anti-wear performance is excellent, high to polar material adhesive strength and good
Good low temperature flexibility.Dimer acid PA PUR has very high added value, and market demand is increasing in recent years, in print
The industries such as brush packaging, clothes, shoemaking, auto industry, electronics encapsulation, material contracting with heat and machinery have a wide range of applications.Dimerization
The representative patents of acid type polyamide hot have CN102703021, CN102807837, CN103468198 etc., these patents
The polyamide hot being previously mentioned highlights the excellent properties of the aspects such as each leisure is high temperature resistant, weatherability, bonding force are strong.
Pressure sensitive adhesive（Pressure sensitive adhesive, PSA）, refer to that a class is slightly pressed to presser sensor, finger pressure
Power can bonding with adherend it is not necessary to a class adhesive using solvent or other supplementary means.Hot-fusible pressure-sensitive adhesive be continue molten
Third generation pressure sensitive adhesive product after formulation and emulsion-type pressure-sensitive, than the above two, thermotropic pressure sensitive glue is solvent-free, more favorably
In environmental protection and safety in production, production efficiency is high, and production cost is relatively low, so current countries in the world positive Devoting Major Efforts To Developing heat molten type pressure
Quick glue.It is matrix resin that hot-fusible pressure-sensitive adhesive typically adopts the rubber such as SBS, SIS, polyisobutene or polyacrylate resin, mesh
Front open report does not also do the pressure sensitive adhesive of matrix resin with regard to polyamide.
Content of the invention
The main object of the present invention, it is desirable to provide a kind of have polyamide hot of pressure-sensitive and preparation method thereof, institute
The polyamide hot pliability of preparation is high, and substrate bonding power is high, to being applied to the life of thermotropic pressure sensitive adhesive tape, sticker
Produce.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of PUR with pressure-sensitive, high-temperature fusion
(150 DEG C) of viscosity is 1500～15000mPa s, and shore hardness is 10～40, and tensile strength is 0.1～1MPa, extension at break
Rate be ＞ 1000% it is characterised in that：Formed by the composition polycondensation of mole percent by following：30%～45% dimeric dibasic acid, 5%～
20% aliphatic dicarboxylic acid, 20%～30% aliphatic diamine, 15%～25% polyetheramine, 0.01%～0.06% end-capping reagent and 0.01%
～0.1% acid catalyst, the molal quantity of described aliphatic dicarboxylic acid is less than or equal to the 40% of dimeric dibasic acid molal quantity.
Further, (150 DEG C) of this PUR high temperature melt viscosity is 2000～13000 mPa s；Shore hardness is 15
～35；Tensile strength is 0.15～0.9MPa；Elongation at break is ＞ 1500%；The mole percent of end-capping reagent be 0.01%～
0.02%, the mole percent of acid catalyst is 0.05%～0.1%；The molal quantity of described aliphatic dibasic acid be less than or
Equal to dimeric dibasic acid molal quantity 35%.
Further, in described dimeric dibasic acid, mass fraction shared by tripolymer is 5%～10%, mass fraction shared by dimer acids
Mass fraction shared by 80%～90%, monomer acids is 5%～10%.
Further, described dimeric dibasic acid is C16～C20 unsaturated aliphatic dimeric dibasic acid；Described aliphatic dicarboxylic acid is
C6～C12 aliphatic dicarboxylic acid；Described aliphatic diamine is spreading out of C2～C8 aliphatic diamine or C2～C8 aliphatic diamine
Biological；Described polyetheramine is containing 2～3 Amino End Group, and molecular weight is 100～3000 polyether polyamine；Described end-capping reagent is C2
～C20 aliphatic mono-acid or the derivative of C2～C20 aliphatic mono-acid；Described acidic catalyst is phosphoric acid, hypophosphorous acid, phosphorous acid
With one of ortho phosphorous acid or arbitrarily several mixtures.
Further, described dimeric dibasic acid be C18 unsaturated aliphatic dimeric dibasic acid, be by dimerized linoleic acid, dimerization oleic acid,
Derived from dimerization leukotrienes, dimerization behenic acid, dimerization elaidic acid and dimerization eleostearic acid；Described polyether polyamine is the trade mark D-230, D-
400th, one of D-2000, T-403 or arbitrarily several mixtures；Described C6～C12 aliphatic dicarboxylic acid be suberic acid,
One of azelaic acid, decanedioic acid and dodecanedioic acid or arbitrarily several mixtures；Described C2～C8 aliphatic diamine is second
One of diamines, pentanediamine and 2 methyl pentamethylenediamine or arbitrarily several mixtures；Described end-capping reagent is C12～C20 fat
Race's mono-acid.
Further, described C6～C12 aliphatic dicarboxylic acid is decanedioic acid；Described C2～C8 aliphatic diamine is 2- first
Base pentanediamine；Described end-capping reagent is stearic acid.
The present invention also provides a kind of preparation method of the PUR with pressure-sensitive, comprises the steps：Carry at one
Dimeric dibasic acid, aliphatic dicarboxylic acid, end-blocking is added in thermometer, the reaction bulb of mechanical agitator, condenser pipe and nitrogen access tube
Agent, polyetheramine and acid catalyst, then, load aliphatic diamine, it is anti-oxidant to be passed through nitrogen, stirring in constant pressure addition pipe
Heat temperature raising simultaneously, when the temperature in reaction bulb reaches 130 DEG C, starts to drip aliphatic diamine, drips in 1h, dropping
When keep the temperature of reaction bulb to be 125-135 DEG C, if temperature, more than 140 DEG C, should stop or slow down rate of addition, until by fat
Fat race diamines drips, and after completion of dropwise addition, the heating rate according to 20 DEG C/h slowly rises high reaction temperature, starts to be to slowly warm up to
240 DEG C, in temperature-rise period, there is water to distillate, when reaction temperature reaches 240 DEG C, keep this temperature section 1h, and measure reaction distillating
Water, reach theoretical value 90% when, can start to carry out vacuumizing decompression, vacuum ＜ 100Pa with vavuum pump, be kept stirring for speed
Rate, completes whole polycondensation reaction in the state of high vacuum, releases vacuum and terminate to react after reaction 3h；Finally, melting is poly-
Amide resin is poured on tetrachloro-ethylene plate, obtains yellow adhesive tape, and drying at 50 DEG C completes for 24 hours.
The invention has the beneficial effects as follows：The polyamide hot high temperature melt viscosity that the present invention has pressure-sensitive is higher, soft
Toughness is high, high to substrate bonding power it is adaptable to process industry pressure-sensitive tape and sticker.
Specific embodiment
Hereinafter the principle and feature of the present invention is described, example is served only for explaining the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1
Add 145.70g C in one with thermometer, the 500mL four-hole boiling flask of agitator, condenser pipe and nitrogen tube16
Unsaturated aliphatic dimeric dibasic acid, 5.10g decanedioic acid, 23.20g polyetheramine D-230,58.00g polyetheramine D-2000,2.20gC12Fat
Fat race mono-acid, 0.20g ortho phosphorous acid, and 10.40g2- making methylpentamethylenediamine diamine is encased in constant pressure funnel, it is passed through nitrogen and stir
Mix and begin to warm up, in 60 minutes, temperature is raised to 120 DEG C, and starts to be slowly added dropwise 2 methyl pentamethylenediamine in this temperature, 60 points
Completion of dropping in clock, now temperature be raised to 130 DEG C, and become salt 2 hours at this temperature, then slowly heat up again, in this process
In have water and steam, in 3 hours, temperature is raised to 240 DEG C, keeps 5 hours at this temperature, then vacuumizes 3 hours with vavuum pump
It is 200Pa to pressure, finally discharging under nitrogen protection, obtain light yellow adhesive tape.
Embodiment 2
Add 113.60gC in one with thermometer, the 500mL four-hole boiling flask of agitator, condenser pipe and nitrogen tube18
Unsaturated aliphatic dimeric dibasic acid, 23.10g suberic acid, 35.40g polyetheramine D-230,1.00gC16Aliphatic mono-acid, 0.20g phosphorus
Acid, and 11.20g2- making methylpentamethylenediamine diamine is encased in constant pressure funnel, it is passed through nitrogen gas stirring and begins to warm up, in 60 minutes
Temperature is raised to 120 DEG C, and starts to be slowly added dropwise 2 methyl pentamethylenediamine in this temperature, completion of dropping in 60 minutes, now temperature
It is raised to 130 DEG C, and becomes salt 2 hours at this temperature, then slowly heat up again, have water in the process and steam, 3 hours interior temperatures
Degree be raised to 240 DEG C, at this temperature keep 5 hours, then with vavuum pump vacuumize 3 hours be 200Pa to pressure, finally in nitrogen
Gas shielded bottom discharge, obtains light yellow adhesive tape.
Embodiment 3
Add 165.10gC in one with thermometer, the 500mL four-hole boiling flask of agitator, condenser pipe and nitrogen tube20
Unsaturated aliphatic dimeric dibasic acid, 1.20g azelaic acid, 78.40g polyetheramine D-2000,1.40gC20Aliphatic mono-acid, 0.50g phosphorous
Acid, and 20.60g2- making methylpentamethylenediamine diamine is encased in constant pressure funnel, it is passed through nitrogen gas stirring and begins to warm up, in 60 minutes
Temperature is raised to 120 DEG C, and starts to be slowly added dropwise 2 methyl pentamethylenediamine in this temperature, completion of dropping in 60 minutes, now temperature
It is raised to 130 DEG C, and becomes salt 2 hours at this temperature, then slowly heat up again, have water in the process and steam, 3 hours interior temperatures
Degree be raised to 240 DEG C, at this temperature keep 5 hours, then with vavuum pump vacuumize 3 hours be 200Pa to pressure, finally in nitrogen
Gas shielded bottom discharge, obtains light yellow adhesive tape.
Embodiment 4
Add 138.30g bis- in one with thermometer, the 500mL four-hole boiling flask of agitator, condenser pipe and nitrogen tube
Poly- linoleic acid, 3.90g dodecanedioic acid, 15.20g polyetheramine D-230,24.00g polyetheramine D-2000,6.20g stearic acid,
0.20g hypophosphorous acid, and 8.50g2- making methylpentamethylenediamine diamine is encased in constant pressure funnel, it is passed through nitrogen gas stirring and begin to warm up, in
In 60 minutes, temperature is raised to 120 DEG C, and starts to be slowly added dropwise 2 methyl pentamethylenediamine in this temperature, completion of dropping in 60 minutes,
Now temperature is raised to 130 DEG C, and becomes salt 2 hours at this temperature, then slowly heats up again, has water in the process and steam, and 3
Hour in temperature be raised to 240 DEG C, at this temperature keep 5 hours, then with vavuum pump vacuumize 3 hours be 200Pa to pressure,
Last discharging under nitrogen protection, obtains light yellow adhesive tape.
Embodiment 5
Add 127.70g bis- in one with thermometer, the 500mL four-hole boiling flask of agitator, condenser pipe and nitrogen tube
Poly- behenic acid, 13.20g decanedioic acid, 2.20g polyetheramine T-403,33.00g polyetheramine D-2000,3.80g stearic acid, 0.20g time
Phosphorous acid, and 17.60g2- making methylpentamethylenediamine diamine is encased in constant pressure funnel, it is passed through nitrogen gas stirring and begins to warm up, in 60 points
In clock, temperature is raised to 120 DEG C, and starts to be slowly added dropwise 2 methyl pentamethylenediamine in this temperature, completion of dropping in 60 minutes, now
Temperature is raised to 130 DEG C, and becomes salt 2 hours at this temperature, then slowly heats up again, has water in the process and steam, 3 hours
Interior temperature is raised to 240 DEG C, at this temperature keep 5 hours, then with vavuum pump vacuumize 3 hours be 200Pa to pressure, finally
Discharging under nitrogen protection, obtains light yellow adhesive tape.
Comparative example
This sample is conventional commercial polyacrylate PUR sample, and its external appearance characteristic is：Amber square solid.By its
Put in 150 DEG C of baking oven, melted, to be melted complete, the sample of melting is poured on tetrachloro-ethylene plate, obtains amber
Film, is tested after being dried 24 hours at 50 DEG C.
By the following method the properties of the prepared sample of embodiment 1-5 and comparative example are carried out contrast test：
Melt viscosity is tested:Using the melt viscosity of Brkfield DV-E type rotation viscometer test sample, weigh
10.0g polyamide hot sample, selects the rotor of model S27 during test, temperature control is at 150 DEG C, and constantly regulate rotation
Rotational speed rate, so as to test value is located in 10%～90% range of linearity, records measured value, viscosity unit after stablizing：mPa.s,
150℃.
Shore hardness is tested:According to ASTM D-2240-05 test.
Tensile strength and test of elongation rate:Sample is made dumbbell shape according to according to standard ASTM-D638-2003, measurement
Carry out tensile property test, tensile strength unit after thickness：MPa；Percentage elongation unit：%.
Shear strength test:According to the sample preparation of standard ASTM-D1002-72, material is Al, nylon66 and PBT, overlapping area
For 12.5 × 25 (mm2), after being placed in 12h under test condition after cooling, carry out the performance test of shear strength.Shear strength unit：
MPa.
The properties of sample contrast test that embodiment 1～5 and comparative example are obtained the results are shown in Table 1.
Table 1
As it can be seen from table 1 the polyamide synthesized by the present invention has higher melt viscosity and pliability, and
Polyacrylate hot-fusible pressure-sensitive adhesive is above to various substrate bonding power, so the polyamide hot synthesized by the present invention is in pressure
The upper prospect of manufacture application of sensitive adhesive tape and sticker is preferable.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvement made etc., should be included within the scope of the present invention.
Claims (2)
1. a kind of PUR with pressure-sensitive, is 11400mPa s in 150 DEG C of high temperature melt viscosity, and shore hardness is 32,
Tensile strength be 0.8MPa, elongation at break be 1700% it is characterised in that：Formed by the composition polycondensation of following weight portion：Two
Poly- behenic acid 127.70, decanedioic acid 13.20, polyetheramine T-403 2.20, polyetheramine D-2000 33.0, stearic acid
3.80, ortho phosphorous acid 0.20,2 methyl pentamethylenediamine 17.60.
2. a kind of preparation method of the PUR with pressure-sensitive described in preparation claim 1, comprises the steps：At one
With addition dimerization behenic acid, decanedioic acid, polyethers in thermometer, the reaction bulb of mechanical agitator, condenser pipe and nitrogen access tube
Amine T-403, polyetheramine D-2000, stearic acid, ortho phosphorous acid, then, load 2 methyl pentamethylenediamine in constant pressure addition pipe, are passed through
Nitrogen is anti-oxidant, stirring heat temperature raising simultaneously, when the temperature in reaction bulb reaches 130 DEG C, starts to drip 2 methyl pentamethylenediamine,
Drip in 1h, during dropping, keep the temperature of reaction bulb to be 125-135 DEG C, if temperature, more than 140 DEG C, should stop or slow down
Rate of addition, until 2 methyl pentamethylenediamine is dripped, after completion of dropwise addition, the heating rate according to 20 DEG C/h slowly raises reaction
Temperature, starts to be to slowly warm up to 240 DEG C, has water to distillate in temperature-rise period, when reaction temperature reaches 240 DEG C, keeps this temperature
Section 1h, and measure the water that distillates of reaction, reach theoretical value 90% when, can start to carry out vacuumizing decompression, vacuum with vavuum pump
Degree ＜ 100Pa, is kept stirring for speed, completes whole polycondensation reaction, release vacuum and terminate after reaction 3h in the state of high vacuum
Reaction；Finally, the polyamide of melting is poured on tetrachloro-ethylene plate, obtains yellow adhesive tape, be dried 24 hours at 50 DEG C
Complete.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106750330A (en) * | 2016-11-14 | 2017-05-31 | 烟台德邦科技有限公司 | A kind of preparation method of polyester amide hot melt adhesive |
| CN107418503A (en) * | 2017-08-24 | 2017-12-01 | 安徽省鸿鑫生物科技有限公司 | A kind of vehicle glass pad pasting light solidifying hot-melt adhesive and preparation method thereof |
| CN109679568A (en) * | 2018-12-07 | 2019-04-26 | 苏州市邦岑新材料股份有限公司 | A kind of water soluble polyamide hot melt adhesive |
| CN109652004A (en) * | 2018-12-17 | 2019-04-19 | 天津海虹科技有限公司 | A kind of preparation method of fabrication polyamide binder |
| CN109605878A (en) * | 2018-12-17 | 2019-04-12 | 吕拴力 | A kind of fabrication polyamide adhesive material |
| CN109652003A (en) * | 2018-12-17 | 2019-04-19 | 天津海虹科技有限公司 | A kind of fabrication polyamide binder |
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| 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 |
| CN104704079B (en) * | 2011-09-06 | 2016-08-24 | 弗林特贸易公司 | Hot-melt adhesive antifoaming agent |
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Address after: No.3-3, Kaifeng Road, Yantai Economic and Technological Development Zone, Shandong Province 264006 Patentee after: Yantai Debang Technology Co.,Ltd. Address before: No.98 Jinshajiang Road, Yantai Development Zone, Shandong Province 264006 Patentee before: DARBOND TECHNOLOGY Co.,Ltd. |
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