CN111040712A - Preparation method of high-strength sweat-resistant polyurethane hot melt adhesive - Google Patents
Preparation method of high-strength sweat-resistant polyurethane hot melt adhesive Download PDFInfo
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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Abstract
The invention relates to a preparation method of a high-strength sweat-resistant polyurethane hot melt adhesive, which comprises the following steps: 15-30 parts of polyester polyol, 30-60 parts of polyether polyol, 15-30 parts of acrylic resin and 5-10 parts of expanded chain are dehydrated for 2 hours at 120 ℃ and-0.095 MPa, after the dehydration is finished, 15-20 parts of isocyanate, 0.2-1.0 part of antioxidant and 0.001-0.1 part of catalyst are added and stirred at the rotating speed of 500 plus materials and 1000 revolutions per minute, the mixture is reacted for 1-3 hours at the temperature of 100 plus materials and 120 ℃, and the mixture is defoamed for 30min, discharged, sealed and packaged to prepare the high-strength sweat-resistant polyurethane hot melt adhesive; the invention may present several advantages: (1) excellent sweat corrosion resistance; (2) excellent bonding strength to surface energy materials (3) good drop resistance: (4) the initial adhesion strength is high.
Description
Technical Field
The invention relates to a preparation method of a high-strength sweat-resistant polyurethane hot melt adhesive, belonging to the field of chemical adhesives.
Technical Field
As is well known, PUR has excellent high and low temperature resistance and weather resistance, and can be used for dispensing adhesive lines of 1mm or less, and thus is widely used for bonding of narrow-bezel mobile phones or flat panels.
However, the traditional polyurethane hot melt adhesive has a plurality of serious defects, such as low initial bonding strength, low adhesion to materials which are difficult to bond, such as PP, PA, stainless steel, nickel-plated metal and the like, and poor aging resistance, and a core defect is poor sweat corrosion resistance, which greatly affects the application range. With the trend of increasingly popularizing, miniaturizing and lightening wearing products such as mobile phones and the like, sweat corrosion poses higher challenges to product quality, and at present, a plurality of cases of mobile phone sealing failure caused by sweat corrosion have occurred. Therefore, various large mobile phone brand manufacturers at home and abroad have put forward the requirement on sweat corrosion resistance on the adhesive.
Therefore, the development of a material having high strength and sweat resistance and simultaneously having excellent adhesion to a hardly adhesive material is an urgent need in this field and also has a great market potential.
Disclosure of Invention
In order to solve the problems of poor sweat resistance and poor adhesion to materials difficult to adhere in the prior art, the invention provides the high-strength sweat resistance polyurethane hot melt adhesive and the preparation method thereof.
The mechanism of the polyurethane hot melt adhesive of the invention for excellent adhesion to various difficult-to-stick base materials and sweat resistance is as follows:
it is known that mussel adhesive protein mucus secreted by marine mussels can firmly adhere to the surface of various substrates even under the action of great wave scouring. It was found that mussels are capable of achieving strong adhesion and excellent salt spray resistance because the mussel adhesion protein they secrete contains catechol groups.
The invention adopts dopamine as raw material to introduce catechol structure into polyurethane structure to realize adhesion to various non-sticky substrates and sweat resistance, and introduces polycaprolactone structure into molecular weight, which has synergistic effect with catechol structure, and has high strength, excellent flexibility and shock resistance and drop resistance after reacting with polyisocyanate. The adopted acrylic resin contains active groups capable of reacting with isocyanate, and the active groups are grafted and polymerized into a molecular structure, so that the crystallinity of the hot melt adhesive is effectively improved, and the function of quick positioning is realized. Therefore, the polyurethane hot melt adhesive not only has excellent adhesion to various base materials including various difficult-to-adhere base materials, but also has excellent sweat corrosion resistance, and the comprehensive performance is very excellent.
The technical scheme of the invention is as follows: a preparation method of a high-strength sweat-resistant polyurethane hot melt adhesive comprises the following preparation steps: a. 1mol of polycaprolactone triol and 2mol of AC2O, 1mol of oxalic acid and 0.1mol of DMAP in CH2CL2Stirring and reacting for 96h at the temperature of 20 ℃, washing and drying the solution by hydrochloric acid, sodium bicarbonate solution and water after the reaction is finished, and eluting by ethyl acetate-cyclohexane solution after chromatographic separation to obtain a target product 1
b. Dissolving the target product 1 and dopamine in dichloromethane, reacting for 4h at 180-240 ℃ and-0.1 MPa, and eluting to obtain the target product 2
c. The target product 2 is deprotected under the action of methanol and sodium bicarbonate, and the target product 3 is obtained by elution
Namely, the self-made chain extender, L, m and n are 0,1,2,3 and 4, and the reaction process is as follows:
d. and D, dehydrating 15-30 parts of polyester polyol, 30-60 parts of polyether polyol, 15-30 parts of acrylic resin and 5-10 parts of the target product obtained in the step C at 120 ℃ and under-0.095 MPa for 2h, adding 15-20 parts of isocyanate, 0.2-1.0 part of antioxidant and 0.001-0.1 part of catalyst into the mixture, stirring the mixture at the rotating speed of 500 plus materials and 1000 rpm, reacting the mixture for 1-3h at the temperature of 100 plus materials and 120 ℃, defoaming the mixture for 30min, discharging the mixture, sealing and packaging the mixture to obtain the high-strength sweat-resistant polyurethane hot melt adhesive.
When the adhesive is used, the heating system is started at the temperature of 100-.
Further, the isocyanate in the step d is at least one of toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate and hydrogenated MDI. Preferably one or more of 4,4' -diphenylmethane diisocyanate, toluene diisocyanate TDI-80/TDI-100 commercially available from Wahua corporation, and HDI trimer Desmodur N330 manufactured by Germany Bayer corporation.
Further, the catalyst in the step d is at least one of dibutyltin dilaurate, stannous octoate, triethylamine, triethylenediamine and zinc naphthenate.
Further, the polyester polyol in step d is prepared by polymerizing adipic acid and at least one diol selected from 1, 4-butanediol, neopentyl glycol, diethylene glycol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, 2, 4-trimethyl-1, 3-pentanediol (TMPD) -series polyester polyols, 3-methyl-1, 5-pentanediol, and 3-methyl-1, 5-pentanediol. The polyadipic acid hexanediol is preferably XCP-3000H available from Jiangsu Sichuan chemical company, the hydroxyl value of the polyadipic acid hexanediol is 35-39mgKOH/g, the acid value of the polyadipic acid hexanediol is 0.1-0.8mgKOH/g, the polyadipic acid-1, 4-butanediol diol is preferably POL-356T available from Qingdao Yutian, the hydroxyl value of the polyadipic acid hexanediol is 35-39mgKOH/g, the acid value of the polyadipic acid hexanediol is 0.1-0.8mgKOH/g, the polyadipic acid-2, 2, 4-trimethyl-1, 3-pentanediol-diol is preferably HJ-7200 available from Changtai Dafu, the hydroxyl value of the polyadipic acid hexanediol is 53-59mgKOH/g, the acid value is less than 0.5mgKOH/g, and the polyether polyol in the step d is polyoxypropylene diol, polyoxypropylene-oxyethylene diol, polytetrahydrofuran ether diol, polyoxypropylene-ethylene oxide diol, polytetrahydrof, Polycaprolactone diol and polycarbonate diol, preferably one or two of PTMG2000, PTMG3000, PPG240, PPG220 and PPG 210.
The polyol adopted by the invention has the beneficial effects that the polyol has a mixed composition of a plurality of crystalline or amorphous polyols, and the relationship between the initial bonding strength and the open time can be balanced to obtain excellent performance.
Further, the acrylic resin in the step d is one of DB808, DB69 and DB29 produced by Nicotiana tabacum.
The acrylic resin adopted by the invention has a special structure, and active groups of the acrylic resin can be reacted with isocyanate to be grafted on a molecular chain, so that the initial bonding strength is improved, and the final strength is not reduced.
Further, the antioxidant in step d is at least one of commercially available antioxidant 264, antioxidant 1010 and antioxidant 1076.
The invention relates to a high-strength sweat-resistant polyurethane hot melt adhesive which not only has excellent sweat corrosion resistance, but also has excellent adhesion to various materials, more importantly, the high-strength sweat-resistant polyurethane hot melt adhesive also has good adhesion to extremely low surface energy materials, has comprehensive performance exceeding that of the similar adhesives sold in the market, and can completely meet the rigorous requirements of high-end electronic products such as mobile phones, communication equipment and the like.
The high-strength sweat-resistant polyurethane hot melt adhesive provided by the invention can embody several advantages: (1) excellent sweat corrosion resistance, and the strength attenuation of the fabric is less than 5 percent when the fabric is soaked in an environment simulating sweat for 21 d; (2) excellent adhesion strength to surface energy materials: the bonding strength of the PP material is higher than 5MPa, and the bonding strength of the glass fiber-containing PA is higher than 5 MPa; (3) the drop resistance is good: the roller falls more than 500 times; (4) the initial adhesion strength is high: the adhesive strength of sizing for 5min is higher than 0.5 MPa. The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Detailed Description
Example 1:
1) polycaprolactone triol with molecular weight of 310 is used as an initiator to prepare a chain extender through the following 3 steps of reaction,
2) 10 parts of polyester polyol XCP-3000H, 5 parts of HJ-7200, 60 parts of polyether polyol PPG220, 30 parts of acrylic resin DB808, 5 parts of self-made chain extender, 120 ℃ and 0.095MPa are dehydrated for 2 hours, after the dehydration is finished, 15 parts of 4,4' -diphenylmethane diisocyanate MDI-100, 2640.2 parts of antioxidant and 0.1 part of dimorpholinodiethyl ether (DMDEE) are added to react at 110 ℃ for 1 hour, the defoaming is carried out for 30 minutes, the materials are discharged, and the sealing and the packaging are carried out, so that the high-strength sweat-resistant polyurethane hot melt adhesive is prepared.
Example 2:
1) polycaprolactone triol with molecular weight of 500 as an initiator is subjected to the following 3-step reaction to prepare a chain extender,
2) 30 parts of polyester polyol POL-356T, 20 parts of polyether polyol PPG210, 10 parts of polyether polyol PPG240, 15 parts of acrylic resin DB69, 10 parts of self-made chain extender, 120 ℃ and-0.095 MPa are dehydrated for 2 hours, after dehydration is finished, 15 parts of 4,4' -diphenylmethane diisocyanate MDI-100, 2 parts of toluene diisocyanate TDI-100, 1 part of antioxidant 1010 and 0.001 part of triethylene diamine are added to react for 1 hour at 110 ℃, defoaming is carried out for 30 minutes, discharging is carried out, sealing and packaging are carried out, and the high-strength sweat-resistant polyurethane hot melt adhesive is prepared.
Example 3:
1) polycaprolactone triol with molecular weight of 500 as an initiator is subjected to the following 3-step reaction to prepare a chain extender,
2) 20 parts of polyester polyol POL-3000H, 5 parts of HJ-7200, 20 parts of polyether polyol PPG210, 25 parts of polyether polyol PPG220, 20 parts of acrylic resin DB29, 8 parts of self-made chain extender, and 0.095MPa at 120 ℃ for dehydration for 2H, after dehydration, 20 parts of 4,4' -diphenylmethane diisocyanate MDI-100, 0.5 part of antioxidant 1076, and 0.005 part of triethylenediamine are added for reaction at 110 ℃ for 1H, and the polyurethane hot melt adhesive with high strength and sweat resistance is prepared after deaeration for 30min, discharging, sealing and packaging.
Comparative example:
the formula and production process of the traditional moisture curing PUR adhesive are as follows: adding 20 parts of polyether polyol PPG210 and 45 parts of polyester polyol POL-356T into a reaction kettle, stirring at the rotating speed of 500 r/min, and carrying out vacuum dehydration at 120 ℃ for 2 hours with the vacuum degree kept at-0.09 MPa. Then cooling to 80 ℃, adding 15 parts of 4,4' -diphenylmethane diisocyanate MDI while stirring, then slowly heating, controlling the temperature at 80 ℃, simultaneously filling nitrogen for protection, and reacting for 2.5 hours. After the content of NCO% reaches the design value by sampling and analysis, 15 parts of terpene tackifying resin, 0.1 part of dibutyltin dilaurate serving as a catalyst and 0.4 part of triethylene diamine are added. Vacuumizing at 110 deg.C until no bubbles appear, discharging, hermetically packaging, and standing. When the glue is used in the process, a heating system is started firstly, the temperature is set to be 100-130 ℃, a glue gun is used for gluing, the gluing process is guaranteed to be completed within the opening time, and then the test is carried out according to the regulations. The adhesion strength was measured after standing for 7 days after the application of the adhesive. The highest strength is generally achieved by curing at room temperature for 7 days.
The polyurethane hot melt adhesives prepared in the above examples 1 to 3 and the polyurethane hot melt adhesives prepared in the comparative examples were subjected to comparative tests according to adhesive test standards, and the tests were respectively as follows: the data results of the decay rate of the adhesive strength with the soaking time of artificial sweat, the adhesive strength to PP and PA containing glass fiber, tensile strength, elongation at break, peel strength, cold and hot impact, salt spray test and double 85 aging are shown in table 1, table 2 and table 3. The decay rate of the bonding strength along with the soaking time of the artificial sweat is used for representing the sweat corrosion resistance, which is the core consideration index of the invention. In addition, the flexibility, the bonding strength and the impact resistance of the invention are respectively represented by the numerical values of tensile strength, elongation at break, shear strength, peel strength and cold and hot impact property in the table 2; the salt spray resistance and the thermal aging resistance are characterized by the values of the test items in Table 3.
Table 1 decay rate (sweat resistance) test of bond strength with artificial sweat soak time comparison:
| sample (I) | Soaking for 1d | Soaking for 5d | Soaking for 7d | Soaking for 15d |
| Example 1 | 100％ | 1％ | 2.2％ | 2.3％ |
| Examples2 | 100％ | 0.3％ | 0.7％ | 0.8％ |
| Example 3 | 100％ | 0.4％ | 1％ | 1.3％ |
| Comparative example | 100％ | 30.5％ | 55.7％ | 70.2％ |
The test method comprises the following steps: soaking the sample in artificial simulated sweat, packaging (sealing) with PE bag, placing in a constant temperature and humidity box with 45 deg.C and 55% RH, taking out, air drying, testing corresponding shear strength, and calculating attenuation rate.
Table 2 examples and comparative examples mechanical property tests were compared:
table 3 comparison of the salt spray resistance and aging resistance tests of the examples with the comparative examples:
performance test analysis of the embodiments 1 to 3 and the comparative example shows that the high-strength sweat-resistant polyurethane hot melt adhesive prepared by the invention has good sweat corrosion resistance, good bonding strength, excellent flexibility, cold and hot impact resistance, salt mist resistance and aging resistance, and simultaneously has excellent bonding performance on difficult-to-bond materials, so that the polyurethane hot melt adhesive provided by the invention can meet strict requirements of sweat resistance, high bonding strength and high reliability in the manufacturing fields of mobile phones, handheld communication equipment, wearable products and the like, and simultaneously solves the problem of poor adhesion on the difficult-to-bond materials.
The above description is only exemplary of the present invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope.
Claims (4)
1. A preparation method of a high-strength sweat-resistant polyurethane hot melt adhesive is characterized by comprising the following preparation steps: 15-30 parts of polyester polyol, 30-60 parts of polyether polyol, 15-30 parts of acrylic resin and 5-10 parts of expanded chain are dehydrated for 2 hours at 120 ℃ and-0.095 MPa, after the dehydration is finished, 15-20 parts of isocyanate, 0.2-1.0 part of antioxidant and 0.001-0.1 part of catalyst are added and stirred at the rotating speed of 500 plus materials and 1000 revolutions per minute, the mixture is reacted for 1-3 hours at the temperature of 100 plus materials and 120 ℃, and the mixture is defoamed for 30min, discharged, sealed and packaged to prepare the high-strength sweat-resistant polyurethane hot melt adhesive;
the preparation steps of the chain extender comprise:
a. 1mol of polycaprolactone triol and 2mol of AC2O, 1mol of oxalic acid and 0.1mol of DMAP in CH2CL2Stirring and reacting for 96 hours at the temperature of 20 ℃, washing and drying the solution by using hydrochloric acid, sodium bicarbonate solution and water after the reaction is finished, and eluting by using ethyl acetate-cyclohexane solution after chromatographic separation to obtain a target product 1;
b. dissolving 1mol of target product 1 and 1mol of dopamine in dichloromethane, reacting for 4h at 180-240 ℃ and-0.1 MPa, and eluting to obtain a target product 2;
1, deprotecting 1mol of the target product 2 and 2mol of methanol under the action of 0.01mol of sodium bicarbonate, and eluting to obtain a target product 3 chain extender;
the molecular formula of the chain extender is as follows:
wherein R is
Wherein L, m, n =0,1,2,3, 4.
2. The method for preparing the high-strength sweat-resistant polyurethane hot melt adhesive according to claim 1, wherein the isocyanate is one or a mixture of toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate and hydrogenated MDI; the catalyst is one of dibutyltin dilaurate, stannous octoate, triethylamine, triethylenediamine and zinc naphthenate.
3. The method for preparing the high-strength sweat-resistant polyurethane hot melt adhesive according to claim 1, wherein the polyester polyol is prepared by polymerizing adipic acid and at least one diol selected from 1, 4-butanediol, neopentyl glycol, diethylene glycol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, 2, 4-trimethyl-1, 3-pentanediol series polyester polyol, 3-methyl-1, 5-pentanediol and 3-methyl-1, 5-pentanediol; the polyether polyol is one or a mixture of two of polyoxypropylene diol, polyoxypropylene-ethylene oxide diol, polytetrahydrofuran ether glycol, polycaprolactone diol and polycarbonate diol with the molecular weight of 1000-4000.
4. The method for preparing the high-strength sweat-resistant polyurethane hot melt adhesive according to claim 1, wherein the acrylic resin is one of DB808, DB69 and DB29 manufactured by Nicoti Federal corporation.
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