CN105778844B - Polyurea adhesive and preparation method thereof - Google Patents
Polyurea adhesive and preparation method thereof Download PDFInfo
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- CN105778844B CN105778844B CN201410820227.0A CN201410820227A CN105778844B CN 105778844 B CN105778844 B CN 105778844B CN 201410820227 A CN201410820227 A CN 201410820227A CN 105778844 B CN105778844 B CN 105778844B
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Abstract
The invention discloses a kind of polyurea adhesive and its manufacturing methods.The polyurea adhesive includes the reaction product that diisocyanate and amino-terminated dimerization amine type polyamide prepolymer aggressiveness are formed, and the amine value of the amino-terminated dimerization amine type polyamide prepolymer aggressiveness is 50-500mgKOH/g, and number-average molecular weight is 1000~10000.Polyurea adhesive of the invention cohesive strength with higher and adhesive strength, good fluidity, water resistance and solvent resistance are excellent, reusable, and can realize multiple reparation.It can be applicable to a variety of bonding occasions such as automobile, cable, electronics.
Description
Technical field
The present invention relates to a kind of polyurea adhesive and its manufacturing methods, particularly by dimerization amine type Polvamide prepolymer
Polyurea adhesive obtained and its manufacturing method.
Background technique
Hot melt adhesive is the good adhesive of a kind of development prospect, mainly includes ethylene copolymer, polyolefins, polyurethane
Class, polyesters and polyamide-based etc., each hot melt adhesive has its advantage.Polyamide is one of internationally recognized top grade
Hot melt adhesive, there are two main classes for polyamide hot, and higher molecular weight is copolyamide, and this kind of polyamide hot has excellent
Different water-fastness and dry cleaning resistance, is widely used in the bonding of fiber, very big in textile industry dosage.Another kind of polyamide
It is to be formed by dimeric dibasic acid and diamine polycondensation, has many advantages, such as that narrow melting range, quick solidifying, adhesive property are excellent, at present extensively
Applied to fields such as shoemaking, automobile, electronics, material contracting with heats.
Studying more hot melt adhesive both at home and abroad now includes a kind of reaction type polyurethane hot melt adhesive, that is, moisturecuring class heat
Melten gel carries out chain extension, further solidification because absorbing the moisture in air after its construction, has finally obtained that cohesive force is strong, bonding is strong
Spend high adhesive.But the disadvantage is that being difficult to be repaired after solidification.
It is well known, however, that reaction type polyurethane hot melt adhesive there are cohesive strength and adhesive strength it is low and solidification after cannot
The shortcomings that modification.
Therefore, the hot melt adhesive that can be modified there are still a kind of pair of cohesive strength and adhesive strength height in this field and after solidifying
Urgent need.
Summary of the invention
It is an object of that present invention to provide a kind of polyurea adhesives, and compared to traditional dimer acid type polyamide adhesive, this is poly-
Urea adhesive cohesive strength with higher and adhesive strength and excellent water-fast, solvent resistance；Compared to polyurethane gluing
Agent, the advantage is that curing time it is short, it is good construction, easily repair etc..
One aspect of the present invention is to provide a kind of polyurea adhesive, it includes diisocyanate and amino-terminated two
The reaction product that polyamine type polyamide prepolymer aggressiveness is formed, the amine value of the amino-terminated dimerization amine type polyamide prepolymer aggressiveness are
50-500mgKOH/g, number-average molecular weight are 1000~10000.
Another aspect of the present invention is to provide the preparation method of above-mentioned polyurea adhesive, it includes:
(i) amino-terminated dimerization amine type polyamide prepolymer aggressiveness is provided, its amine value is 50-500mgKOH/g, and number is divided equally
Son amount is 1000~10000；
(ii) diisocyanate is provided；
(iii) 200-250 DEG C at a temperature of make amino-terminated dimerization amine type polyamide prepolymer aggressiveness and diisocyanate
Reaction.
The present invention by the way that urea bond is introduced into polyamide adhesives, improve polyamide adhesives itself cohesive strength and
Adhesive strength, while the shortcomings that polyurethane adhesive cannot be repaired is overcome, obtain the higher polyureas glue of a kind of comprehensive performance
Stick.Polyurea adhesive of the invention has many advantages, such as construction, Yi Xiufu well, is the good hot melt adhesive of a kind of development prospect.
Specific embodiment
In one preferred embodiment, poly- for synthesizing the amino-terminated dimerization amine type of polyurea adhesive of the present invention
The amine value of amide performed polymer is 100-300mgKOH/g, and number-average molecular weight is 1500~9000, preferably 1500-3500.
In a particularly preferred embodiment, for synthesizing the amino-terminated polyamine of polyurea adhesive of the present invention
Type polyamide prepolymer aggressiveness includes:
(1) sour polymerized unit, it includes:
(a) 95-100 moles of %C10-18Long-chain fat race dicarboxylic acids copolymerization units, and
(b) 0-5 moles of %C2-18Aliphatic monocarboxylic acid, on the basis of the total mole number of sour polymerized unit；And
(2) amine copolymer unit, it includes:
(c) 65-80 moles of % polyamine copolymerization units,
(d) 20-35 moles of %C2-10Aliphatic diamine copolymerization units, and
(e) 0-10 moles of %C5-6Ring diamine, on the basis of the total mole number of amine polymerized unit, wherein amine copolymer unit
Molar ratio with sour polymerized unit is 1.05-1.5:1.
In one more particularly preferred embodiment, for synthesizing amino-terminated two of polyurea adhesive of the present invention
Polyamine type polyamide prepolymer aggressiveness includes:
(1) sour polymerized unit, it includes:
(a) 95-99 moles of %C12-16Long-chain fat race dicarboxylic acids copolymerization units, and
(b) 1-3 moles of %C10-18Aliphatic monocarboxylic acid, on the basis of the total mole number of sour polymerized unit；And
(2) amine copolymer unit, it includes:
(c) 65-80 moles of % polyamine copolymerization units, and
(d) 20-35 moles of %C4-8Aliphatic diamine copolymerization units, on the basis of the total mole number of amine polymerized unit,
The molar ratio of middle amine copolymer unit and sour polymerized unit is 1.05-1.3:1.
In one preferred embodiment, poly- for synthesizing the amino-terminated dimerization amine type of polyurea adhesive of the present invention
Amide performed polymer is by C10-18Long-chain fat race dibasic carboxylic acid monomers, dimerization amine monomers, C2-10Binary aliphatic amine monomers and appoint
The C of choosing5-6Ring diamine monomer is in the C for being used as molecular weight regulator2-18Melt polymerization in the presence of aliphatic monocarboxylic acid and
At.Polymerization reaction carries out at a temperature of preferably 130-240 DEG C generally at 100-250 DEG C.
In one preferred embodiment, it is used to prepare the polyamine of amino-terminated dimerization amine type polyamide prepolymer aggressiveness
Monomer is obtained by dimeric dibasic acid nitrilation plus hydrogen.Has corresponding product supply in the market, the mass content of dimerization amine monomers is 90%
More than.And dimeric dibasic acid is C16~20The dimer of unsaturated fatty acid, such as by linoleic acid, oleic acid, linolenic acid, elaidic acid, soya-bean oil
Dimeric dibasic acid derived from acid, eleostearic acid or appropriate youngster oil.Therefore, dimerization amine monomers are preferably C32~40Dimerization amine monomers.
In one preferred embodiment, it is used to prepare the C of amino-terminated dimerization amine type polyamide prepolymer aggressiveness2~10Rouge
Fat race diamine monomer for example including but be not limited to ethylenediamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, decamethylene diamine or they
Mixture.
In one preferred embodiment, it is used to prepare the ring binary of amino-terminated dimerization amine type polyamide prepolymer aggressiveness
Amine monomers include cycloalphatic diamine, hetero-aromatic ring diamines, aromatic ring diamines, the cyclic compound of amino substitution or their mixing
Object.Specific example includes piperazine, aminoethyl piperazine, cyclohexanediamine, pyridine diamines or their mixture.
In one preferred embodiment, it is used to prepare the C of amino-terminated dimerization amine type polyamide prepolymer aggressiveness10-18It is long
Chain fatty race dibasic carboxylic acid monomers are preferably C10-18Straight-chain aliphatic dibasic carboxylic acid monomers, for example including but be not limited to decanedioic acid,
11 carbon dicarboxylic acids, dodecanedicarboxylic acid, tetradecane diacid and 16-dicarboxylic acid, 18 carbon dicarboxylic acids or they
Mixture.Preferred aliphat dibasic carboxylic acid monomers be dodecanedicarboxylic acid, tetradecane diacid and 16-dicarboxylic acid or
Their mixture.
In one preferred embodiment, C2-18Aliphatic unit acid is as molecular weight regulator, preferably caproic acid, pungent
Acid, capric acid, lauric acid, myristic acid, palmitinic acid, stearic acid, arachidic acid or their mixture.Preferably lauric acid, tristearin
Acid or their mixture.
In one preferred embodiment, in the synthesis technology for preparing amino-terminated dimerization amine type polyamide prepolymer aggressiveness
In, preferably use acid catalysis, such as phosphoric acid, phosphorous acid or the mixed acid of both；Catalyst amount be gross mass 0.01~
0.05wt%, preferably 0.015~0.025wt%.
In one preferred embodiment, it when preparing amino-terminated dimerization amine type polyamide prepolymer aggressiveness, needs tight
Lattice control the molar ratio of amine polymerized monomer and sour polymerized monomer, and generally 1.05~1.5:1, preferably 1.1~1.3:1 guarantee
It is end group that dimerization amine type polyamide prepolymer aggressiveness, which is amino,.
It, will be accurate in a particularly preferred embodiment for preparing amino-terminated dimerization amine type polyamide prepolymer aggressiveness
Dicarboxylic acids (such as C after weighing14Binary acid), polyamine, piperazine, after the comonomers such as phosphoric acid and auxiliary agent precise, investment
In the four-hole boiling flask of 1L.Under nitrogen and stirring condition, 160 DEG C are warming up to, until the component in bottle is completely dissolved；Then slowly
Heating, in 1.5~2 hours, is raised to 240 DEG C by 160 DEG C for temperature in the kettle, while measuring water yield；When water yield reaches reason
By value 80% or more when, carry out decompression step by step；Entire reaction, vacuum reaction time about 2~10 are finally completed under a high vacuum
Hour.Then under nitrogen pressurising to normal pressure, polyamide is fallen in tetrafluoro plate face while hot, particle is cut into after cooling and shaping.
The side that the amine value of amino-terminated dimerization amine type polyamide prepolymer aggressiveness obtained passes through constant-current titration according to the above method
Method test, controls in 50~500mgKOH/g, preferably 100-300mgKOH/g.
Then, by amino-terminated dimerization amine type polyamide prepolymer aggressiveness and di-isocyanate reaction obtained according to the above method
Prepare polyurea adhesive of the invention.
In one preferred embodiment, by with it is two of amido equivalent in above-mentioned dimerization amine type polyamide prepolymer aggressiveness different
Cyanate, which is titrated in the dimerization amine type polyamide prepolymer aggressiveness of melting under the conditions of 200~230 DEG C, to be reacted, and is obtained final
Polyurea adhesive product.
In one preferred embodiment, in order to reduce toxicity volatilization, the present invention is such as poly- using liquefaction diisocyanate
The modified MDI of ether or isoflurane chalcone diisocyanate (IPDI) and other small liquid diisocyanates that volatilize.
The visible trade mark provided by Japanese polyurethane industrial group of the modified liquid diisocyanate of commercialization is
The liquefied mdis such as Millonate-1040, Millionate-1041 and Millionate-MR-P.Isoflurane chalcone diisocyanate
The Related product provided by German Chemische Werke Huls company is then provided.
In a particularly preferred embodiment, polyurea adhesive of the present invention can have following technique to be prepared:
The amino-terminated dimerization amine type polyamide prepolymer aggressiveness accurate weighing of amine value will be tested, and calculated its amino-contained
Number；Then precise contains the diisocyanate that the isocyanates radix of congruent equivalent is counted up to amido, by diisocyanate
It under the conditions of 200~230 DEG C, is added drop-wise in the amino-terminated dimerization amine type polyamide prepolymer aggressiveness of melting, sufficiently reaction 2 is small
When, vacuum defoamation, discharging obtains final product.
In the above-mentioned methods, the isocyanate group in diisocyanate and the amido base in dimerization amine type polyamide prepolymer aggressiveness
It is reacted in sheet by equivalent, preferably with the reaction of 1.0-1.05:1 equivalent proportion.The number-average molecular weight of polyurea adhesive obtained is
10000~40000, preferably 12000~25000, more preferable 15000-21000.
The polyurea adhesive that the present invention obtains cohesive strength with higher and adhesive strength, good fluidity, water resistance and
Solvent resistance is excellent, reusable, and can realize multiple reparation.It can be applicable to a variety of bonding fields such as automobile, cable, electronics
It closes.
Embodiment
Following embodiment and comparative example is for further illustrating the present invention, it is to be understood that these embodiments cannot be used for
It limits the scope of the invention.
Sheet obtained in amino-terminated dimerization amine type polyamide prepolymer aggressiveness and embodiment obtained in following comparative example
Invention polyurea adhesive test performance in accordance with the following methods:
Amine value test: accurately weighing 0.5g sample (being accurate to 0.0001g), with 30ml chloroform-methanol mixed solution, often
Temperature or low-grade fever dissolution, with 0.05N hydrochloric acid standard solution titration to terminal, titration end-point by ZDJ-4A type automatical potentiometric titrimeter from
Dynamic judgement.
Amine value (mgHCL/g)=56.11NV/W
In formula: N: the equivalent concentration of hydrochloric acid standard solution；
V: the volume of hydrochloric acid standard solution, ml；
W: example weight, g.
Softening point test: it is tested by standard GB/T 15332-94.
Adhesive strength test:
Bonding of the PE to PE: the PE material that width is 25mm is placed on thermal-flame quick calcination to PE material softening, so
The polyamide hot of melting is applied on the calcination face PE afterwards, the PE quick-binding of gluing will be applied, it is cooling, it is placed under test condition
After 12h, peel strength performance test is carried out in model GT-AI-3000 tensile testing machine.
Bonding of the Al to Al: being that length is 100mm, width 25mm, is wiped with acetone with a thickness of the aluminum flake surface of 1mm by width
Only, then the polyamide hot of melting is applied on surface-treated aluminium flake, another aluminium flake quick-binding, it is cooling, it sets
Under 10 Kgfs of pressure, after being placed at room temperature for 12h, the survey of peel strength performance is carried out in model GT-AI-3000 tensile testing machine
Examination.
Tensile strength test: it is tested according to standard GB/T 528-2009.
Comparative example 1
By 0.4mol polyamine (trade mark P1074, big purchased from U.S.'s standing grain), 0.1mol hexamethylene diamine, 14 carbon two of 0.49mol
In the investment 2000ml four-hole boiling flask such as first acid, 0.01mol stearic acid and a small amount of antioxidant 1010, it is warming up under nitrogen protection
130℃；After component is completely dissolved in bottle, start slowly heating.240 DEG C are warming up in 1.5~2h；Measure water yield；To
When reaching 80% or more of theoretical water yield, decompression step by step is carried out；Entire reaction is finally completed under a high vacuum, when vacuum reaction
Between about 5~10 hours.Then under 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 adhesives, after tested, ring and ball softening point are 142 DEG C；Amine value 2.0mgKOH/g, number-average molecular weight
It is 13000.
Comparative example A 1
By 0.4mol polyamine (trade mark P1074, big purchased from U.S.'s standing grain), 0.15mol hexamethylene diamine, 14 carbon of 0.49mol
Binary acid, 0.01mol stearic acid and a small amount of antioxidant 1010 etc. are put into 2000ml four-hole boiling flask, are heated up under nitrogen protection
To 130 DEG C；After component is completely dissolved in bottle, start slowly heating.240 DEG C are warming up in 1.5~2h；Measure water yield；
It is to be achieved theory water yield 80% or more when, carry out decompression step by step；Entire reaction, vacuum reaction are finally completed under a high vacuum
Time about 5~10 hours.Then under 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 Polvamide prepolymer, after tested, ring and ball softening point are 140 DEG C；Amine value 150mgKOH/g.Number-average molecular weight
It is 2430.
Embodiment 1
200g A1 performed polymer is accurately weighed, since amine value is 150mgKOH/g, can be calculated, the number containing amido are as follows:
0.535 mole.B component is polyether-modified isocyanates, and Millionate-1040, isocyanate group content is that 23% (quality contains
Amount), it is computed, accurately weighs B component 97.69g, by B component under the conditions of 200~230 DEG C, be slowly dropped into the component A of melting
In, it stirs 2 hours, vacuum defoamation half an hour.Discharging.Obtain product.
Through measuring: softening point is 153 DEG C, number-average molecular weight 17000.
Embodiment 2
200g A1 performed polymer is accurately weighed, since amine value is 150mgKOH/g, can be calculated, the number containing amido are as follows:
0.535 mole.B component selects isoflurane chalcone diisocyanate, is computed, B component 59.46g is accurately weighed, by B component 200
It under the conditions of~230 DEG C, is slowly dropped into the component A of melting, stirs 2 hours, vacuum defoamation half an hour.Discharging.Obtain product.
158 DEG C of softening point are measured, number-average molecular weight 19500.
1 polyamide hot performance of the embodiment of the present invention of table compares
Claims (10)
1. a kind of polyureas hot melt adhesive, it include diisocyanate formed with amino-terminated dimerization amine type polyamide prepolymer aggressiveness it is anti-
Product is answered, the amine value of the amino-terminated dimerization amine type polyamide prepolymer aggressiveness is 50-500mgKOH/g, and number-average molecular weight is
1000~10000.
2. polyureas hot melt adhesive as described in claim 1, which is characterized in that the amino-terminated dimerization amine type polyamide prepolymer
The amine value of aggressiveness is 100-300mgKOH/g, and number-average molecular weight is 1500~9000.
3. polyureas hot melt adhesive as claimed in claim 1 or 2, which is characterized in that the amino-terminated dimerization amine type polyamides
Amine performed polymer includes:
(1) sour polymerized unit, it includes:
(a) 95-100 moles of %C10-18Long-chain fat race dicarboxylic acids copolymerization units, and
(b) 0-5 moles of %C2-18Aliphatic monocarboxylic acid, on the basis of the total mole number of sour polymerized unit；And
(2) amine copolymer unit, it includes:
(c) 65-80 moles of % polyamine copolymerization units,
(d) 20-35 moles of %C2-10Aliphatic diamine copolymerization units, and
(e) 0-10 moles of %C5-6Ring diamine, on the basis of the total mole number of amine polymerized unit, wherein amine copolymer unit and acid
The molar ratio of polymerized unit is 1.05-1.5:1.
4. polyureas hot melt adhesive as claimed in claim 3, which is characterized in that the amino-terminated dimerization amine type polyamide prepolymer
Aggressiveness includes:
(1) sour polymerized unit, it includes:
(a) 97-99 moles of %C12-16Long-chain fat race dicarboxylic acids copolymerization units, and
(b) 1-3 moles of %C10-18Aliphatic monocarboxylic acid, on the basis of the total mole number of sour polymerized unit；And
(2) amine copolymer unit, it includes:
(c) 65-80 moles of % polyamine copolymerization units, and
(d) 20-35 moles of %C4-8Aliphatic diamine copolymerization units, on the basis of the total mole number of amine polymerized unit, wherein amine
Copolymerization units and the molar ratio of sour polymerized unit are 1.05-1.3:1.
5. polyureas hot melt adhesive as claimed in claim 3, which is characterized in that the C5-6Ring diamine includes piperazine, aminoethyl
Piperazine, cyclohexanediamine, pyridine diamines or their mixture.
6. polyureas hot melt adhesive as claimed in claim 1 or 2, which is characterized in that the diisocyanate is two isocyanide of liquid
Acid esters.
7. polyureas hot melt adhesive as claimed in claim 6, which is characterized in that the diisocyanate is diphenyl methane -4,
4'- diisocyanate (MDI), isophorone diisocyanate or their mixture.
8. polyureas hot melt adhesive as claimed in claim 1 or 2, which is characterized in that the isocyanates in the diisocyanate
Base is reacted with the amino in amino-terminated dimerization amine type polyamide prepolymer aggressiveness with 1.0-1.05:1 equivalent proportion, polyureas hot melt adhesive
Number-average molecular weight be 10000~40000.
9. it includes: such as the preparation method of polyureas hot melt adhesive of any of claims 1-8
(i) amino-terminated dimerization amine type polyamide prepolymer aggressiveness is provided, its amine value is 50-500mgKOH/g, number-average molecular weight
It is 1000~10000；
(ii) diisocyanate is provided；
(iii) 200-250 DEG C at a temperature of make amino-terminated dimerization amine type polyamide prepolymer aggressiveness and di-isocyanate reaction.
10. preparation method as claimed in claim 9, which is characterized in that the diisocyanate is liquid diisocyanates.
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| TWI627250B (en) * | 2017-01-04 | 2018-06-21 | 台虹科技股份有限公司 | Adhesive composition and application thereof |
| CN110003423B (en) * | 2019-03-20 | 2022-03-11 | 浙江华峰新材料有限公司 | Modified isocyanate prepolymer, polyurethane composite material, and preparation method and application thereof |
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| DE69937411T2 (en) * | 1999-06-07 | 2008-07-24 | 3M Innovative Properties Co., St. Paul | ADHESIVES BASED ON POLYURE, OBJECTS THEREOF, AND METHOD FOR THEIR PRODUCTION AND USE |
| EP1524282A1 (en) * | 2003-10-15 | 2005-04-20 | Sika Technology AG | Two-component polyurethane composition having high early strength |
| US7163996B2 (en) * | 2003-11-24 | 2007-01-16 | Henkel Corporation | Polyamides |
| CN103184030B (en) * | 2011-12-28 | 2014-11-12 | 上海轻工业研究所有限公司 | Novel polyamide adhesive |
| CA2900317C (en) * | 2013-02-13 | 2019-11-19 | Lubrizol Advanced Materials, Inc. | Water borne polyamide-urea dispersions |
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