CN107987777B - Polyurethane emulsion adhesive containing nano-cellulose whiskers and preparation method thereof - Google Patents
Polyurethane emulsion adhesive containing nano-cellulose whiskers and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
Abstract
The polyurethane emulsion adhesive containing the nanocellulose whiskers adopts the nanocellulose whiskers as a blocking agent, has the effects of reinforcing and inducing polyurethane molecular chain crystallization, improves the initial adhesion of the adhesive, utilizes acetophenone oxime to block isocyanate as a potential reactive group, can further react with an active group of a bonding interface, and improves the bonding strength of the adhesive. The prepared polyurethane adhesive has the excellent performances of high initial viscosity, high crystallization speed, high crystallinity, high bonding strength and the like.
Description
Technical Field
The invention relates to the field of polyurethane adhesives, in particular to a high-performance aqueous polyurethane emulsion adhesive with high initial adhesion, high crystallization speed and high crystallinity and a preparation method thereof.
Background
The water-based polyurethane adhesive gradually becomes the mainstream of the adhesive market because of the advantages of no pollution, easy transportation, friendly working environment and the like. However, the aqueous polyurethane adhesive has the disadvantages of slow drying speed, small initial adhesion, poor water resistance and the like, and particularly, the low initial adhesion seriously affects the construction convenience of the polyurethane adhesive and limits the further development of the aqueous polyurethane adhesive.
The crystallization speed of the polyurethane molecular chain is one of the important factors for determining the initial adhesion of polyurethane. The crystallization speed of the molecular chain is high, the cohesion of the polyurethane molecular chain is increased rapidly in a short time, and the initial adhesion is effectively improved. Moreover, the high crystallization speed can also improve the final bonding strength of the adhesive. Therefore, the improvement of the crystallization speed of the polyurethane molecular chain is one of effective schemes for simultaneously solving the initial adhesion and the final adhesive strength of the waterborne polyurethane, and is also one of the research focuses of the waterborne polyurethane at present.
The nano cellulose whiskers (CNs) are derived from plants, animals and microorganisms, have a long length-diameter ratio of 50-110 and a specific surface area of 150-300 m2The material is a novel nano material which is environment-friendly and has reproducibility, and the theoretical modulus is up to 150 GPa. Moreover, the nanocellulose whisker with the surface rich in hydroxyl is easy to dissolve in water, and is a potentially important nano reinforcing filler of waterborne polyurethane. In addition, the one-dimensional nano cellulose whiskers can also induce polyurethane molecular chains to stretch and arrange along the dimension direction of the polyurethane molecular chains, so that the induced crystallization of the polyurethane molecular chains is realized, and the crystallization speed is improved. However, after the nanocellulose whiskers and the aqueous polyurethane adhesive are simply and mechanically mixed, the nanocellulose whiskers can be reunited due to the strong internal hydrogen bond effect after being stored for a long time, so that the serious sedimentation problem is brought, and the performance of the adhesive is seriously weakened. Therefore, how to avoid the agglomeration of the nano-cellulose whiskers in the waterborne polyurethane, ensure the reinforcing effect of the nano-cellulose whiskers on the polyurethane, promote the nano-cellulose whiskers to exert the effect of improving the crystallization speed of a polyurethane molecular chain is one of the keys for solving the problems of low initial adhesion and low bonding strength of the waterborne polyurethane.
Disclosure of Invention
The invention aims to provide a nano-cellulose whisker-containing aqueous polyurethane emulsion adhesive with high crystallization speed, high initial adhesion and high bonding strength and a preparation method thereof.
The technical solution for realizing the purpose of the invention is as follows:
a preparation method of a polyurethane emulsion adhesive containing nano-cellulose whiskers comprises the following steps:
the method comprises the following steps: under the protection of nitrogen, adding 1mol of poly (hexamethylene adipate) glycol ester dihydric alcohol and 2mol of toluene diisocyanate, stirring for 2-3 h at the temperature of 60-70 ℃, adding 100g of nano cellulose whisker, adding 2wt% of dibutyltin dilaurate, continuously stirring for 1-2 h at the temperature of 80-90 ℃, then reducing the temperature, adding 1mol of sealing agent, and continuously stirring for 2h to obtain a prepolymer A, wherein 2wt% is based on the sum of the poly (hexamethylene adipate) glycol ester dihydric alcohol and the toluene diisocyanate;
step two: under the protection of dry nitrogen, adding 10mol of polyhexamethylene glycol adipate diol with the molecular weight of 4000 and 20mol of toluene diisocyanate into a reaction kettle, heating to 60 ℃, stirring for 2h, adding 2wt% of dibutyltin dilaurate, and continuously stirring for 2h to obtain a prepolymer B, wherein the 2wt% is based on the sum of the polyhexamethylene glycol adipate diol and the toluene diisocyanate;
step three: adding 5mol of dimethylolpropionic acid into the prepolymer B obtained in the step two, heating and stirring, finally adding 2mol of trimethylolpropane and 1mol of diethylene glycol, adjusting the system viscosity to 2000-4000 mPa.s by using acetone, stirring for 3h at the speed of 40r/min, cooling to 50 ℃, adding the prepolymer A obtained in the step one according to the mass ratio of the system to the prepolymer A of 1:1, and continuously stirring for 1h at 40r/min to obtain a polyurethane solution;
step four: and (3) adding the polyurethane solution obtained in the third step into deionized water at a mass ratio of 1:0.5 under stirring at 50r/min, stirring for 1h, and then carrying out reduced pressure distillation to remove the solvent acetone, thereby obtaining the aqueous polyurethane emulsion adhesive containing the nano-cellulose whiskers.
The length of the nano cellulose whisker in the step oneThe ratio of the diameter to the diameter is 200, and the specific surface area is 200m2(ii)/g, the number of surface hydroxyl groups is 30.0OH/nm2。
The structural formula of the prepolymer A obtained in the step one is as follows:
in the first step, the temperature is reduced to 50 ℃, and the added sealing agent is the acetophenone oxime.
In the third step, 5mol of dimethylolpropionic acid is added, and the mixture is stirred for 1-2 hours at the temperature of 60-70 ℃; trimethylolpropane was added in an amount of 2mol and diethylene glycol was added in an amount of 1 mol.
The invention also discloses the polyurethane emulsion adhesive containing the nano-cellulose whiskers, which is prepared by the method.
Compared with the prior art, the invention has the following remarkable advantages:
(1) in the polyurethane emulsion adhesive, the polyester polyol with specific molecular weight is matched with the nano-cellulose whiskers with specific structures, so that the nano-cellulose whiskers are used as a blocking agent and stably dispersed in the polyurethane emulsion adhesive, the nano-reinforcing effect of the nano-cellulose whiskers on the polyurethane adhesive is realized, and the initial adhesion and the bonding strength of the adhesive are improved;
(2) the nano-cellulose whiskers are introduced into the polyurethane emulsion adhesive, so that on one hand, the crystallization speed of the polyurethane adhesive is improved by utilizing the induction effect of the nano-cellulose whiskers on polyurethane molecular chain crystallization, and on the other hand, the nano reinforcement effect of the nano-cellulose whiskers is utilized, so that the initial adhesion of the adhesive is effectively increased, the bonding strength and the heat resistance of the adhesive are improved, and the obtained adhesive has construction convenience and a good using effect.
Drawings
FIG. 1 is a flow chart of a preparation process of the polyurethane emulsion adhesive in example 1 of the present invention.
Detailed Description
A preparation method of a polyurethane emulsion adhesive containing nano-cellulose whiskers comprises the following steps:
the method comprises the following steps: under the protection of nitrogen, adding 1mol of poly hexamethylene adipate glycol ester dihydric alcohol and 2mol of toluene diisocyanate, stirring uniformly, reacting for 2-3 h at the temperature of 60-70 ℃, adding the mixture with the length-diameter ratio of 200 and the specific surface area of 200m2(ii)/g, the number of surface hydroxyl groups is 30.0OH/nm2Adding 2wt% of dibutyltin dilaurate into the nano-cellulose whisker, continuously stirring for 1-2 h at the temperature of 80-90 ℃, then reducing the temperature to 50 ℃, adding 1mol of acetophenone oxime, and continuously stirring for 2h to obtain a prepolymer A, wherein 2wt% is based on the sum of polyadipic acid hexanediol ester dihydric alcohol and toluene diisocyanate.
Step two: under the protection of dry nitrogen, 10mol of polyhexamethylene glycol adipate diol with the molecular weight of 4000 and 20mol of toluene diisocyanate are added into a reaction kettle, the mixture is heated to 60 ℃, stirred for 2h, 2wt% of dibutyltin dilaurate is added, and the stirring is continued for 2h to obtain a prepolymer B, wherein the 2wt% is based on the sum of the polyhexamethylene glycol adipate diol and the toluene diisocyanate.
Step three: and (3) adding 5mol of dimethylolpropionic acid into the prepolymer B obtained in the step two, stirring for 1-2 h at the temperature of 60-70 ℃, finally adding 2mol of trimethylolpropane and 1mol of diethylene glycol, adjusting the system viscosity to 2000-4000 mPa.s by using acetone, stirring for 3h at the speed of 40r/min, cooling to 50 ℃, adding the prepolymer A obtained in the step one in the mass ratio of 1:1, and continuously stirring for 1h at the speed of 40r/min to obtain a polyurethane solution.
Step four: and (3) adding the polyurethane solution obtained in the third step into deionized water at a mass ratio of 1:0.5 under stirring at 50r/min, stirring for 1h, and then carrying out reduced pressure distillation to remove the solvent acetone, thereby obtaining the aqueous polyurethane emulsion adhesive containing the nano-cellulose whiskers.
And (3) carrying out performance test on the prepared aqueous polyurethane emulsion adhesive containing the nano-cellulose whiskers.
(1) Initial adhesion:
a GB/T2790 adhesive 180-degree peel strength test method is adopted. Bending one end of the flexible adhered test piece which is not adhered by glue for 180 degrees, clamping the rigid adhered test piece on the fixed chuck, and clamping the flexible test piece on the other chuck. Care was taken to accurately position the sample between the jaws to ensure that the applied tension was evenly distributed across the width of the sample. The machine was started to separate the upper and lower jaws at a constant rate. The separation rate of the cartridge was 100. + -. 10 mm/min. The rate of separation of the jaws and the force to which the jaws are subjected when they are operated to separate are noted until at least 125mm of the length of the bond is peeled away. The larger the initial adhesion, the better.
Note: in the peeling process, the peeled flexible portion sometimes rubs off on the adhesive bonded portion, and in order to reduce friction, a suitable lubricant such as glycerin or soapy water may be used as long as it does not affect the adherend.
(2) Bonding strength:
the prepared adhesive is tested by referring to a GB 7124-86 adhesive tensile shear strength measuring method. The measuring tool measures the length and width of the faying surface of the test piece to the accuracy of 0.05 mm. The test specimen is symmetrically clamped in an upper clamp and a lower clamp, and the distance from the clamping position to the overlapping end is 50 +/-1 mm. The tester was started and loaded at a steady speed within 5. + -.1 mm/min. The maximum load of shear failure and the type of adhesive failure (cohesive, adhesive, metal) of the test specimen were recorded. The larger the peel strength, the better.
(3) Thermal stability:
adopting a TG test method to carry out thermal stability test on the prepared waterborne polyurethane adhesive, making a TG curve, and obtaining the temperature T corresponding to the thermal weight loss of 5 percent from the curve5％. Wherein, the higher the weight loss temperature is, the better the stability of the adhesive is.
(5) Crystallization property:
based on the test data of DSC, the area enclosed by the DSC curve and the base line is converted into a enthalpy value (crystallization enthalpy. DELTA.H)c) Tabulated, and the temperature of the crystallization peak is taken as the crystallization temperature TcThe half width FWHH of the crystallization peak was recorded as the relative crystallization velocity. T iscLarger indicates that the sample is more easily crystallized, smaller FWHH indicates faster relative crystallization rate,. DELTA.HcThe larger the value, the higher the crystallinity.
The present invention is further illustrated by the following examples and comparative examples.
Example 1
The method comprises the following steps: under the protection of nitrogen, 1mol of poly hexamethylene adipate diol ester diol and 2mol of toluene diisocyanate are added, the mixture is evenly stirred and reacts for 3 hours at the temperature of 60 ℃, 100g of the mixture with the length-diameter ratio of 200 and the specific surface area of 200m is added2(ii)/g, the number of surface hydroxyl groups is 30.0OH/nm2Adding 2wt% of dibutyltin dilaurate into the nano-cellulose whisker, continuously stirring for 1h at the temperature of 90 ℃, then reducing the temperature to 50 ℃, adding 1mol of acetophenone oxime, and continuously stirring for 2h to obtain a prepolymer A, wherein 2wt% of the prepolymer A is based on the sum of polyadipic acid hexanediol ester dihydric alcohol and toluene diisocyanate;
step two: adding 10mol of polyhexamethylene glycol adipate diol with the molecular weight of 4000 and 20mol of toluene diisocyanate into a reaction kettle, heating to 60 ℃, stirring for 2h, adding 2wt% of dibutyltin dilaurate, and continuously stirring for 2h to obtain a prepolymer B, wherein the 2wt% is based on the sum of the polyhexamethylene glycol adipate diol and the toluene diisocyanate;
step three: adding 5mol of dimethylolpropionic acid into the prepolymer B obtained in the step two, stirring for 1h at 70 ℃, finally adding 2mol of trimethylolpropane and 1mol of diethylene glycol, adjusting the system viscosity to 2000mPa & s by using acetone, stirring for 3h at the speed of 40r/min, cooling to 50 ℃, adding the prepolymer A obtained in the step one with the mass ratio of 1:1, and continuously stirring for 1h at 40r/min to obtain a polyurethane solution;
step four: and (3) adding the polyurethane solution obtained in the third step into deionized water at a mass ratio of 1:0.5 under stirring at 50r/min, stirring for 1h, and then carrying out reduced pressure distillation to remove the solvent acetone, thereby obtaining the aqueous polyurethane emulsion adhesive containing the nano-cellulose whiskers.
The preparation flow chart of the waterborne polyurethane emulsion adhesive is shown in figure 1. Adhesive properties are shown in table 1.
Example 2
The process of example 1 was repeated with the indicated amounts of the components, but the first stage temperature in step one was 70 ℃ and the stirring time was 2 h; the temperature of the second section is 80 ℃, and stirring is carried out for 2 hours; the first stage temperature in the third step is 60 ℃, the stirring time is 2 hours, and the system viscosity is 4000mPa & s. Adhesive properties are shown in table 1.
Comparative example 1
The method of example 1 was repeated at the specified contents of each component, but no nanocellulose whiskers were added in step one. Adhesive properties are shown in table 1.
Comparative example 2
The process of example 1 is repeated with the stated contents of the components, but the prepolymer A added in step three has the structure
Adhesive properties are shown in table 1.
Comparative example 3
The process of example 1 is repeated with the indicated amounts of the individual components, but the prepolymer A added in step three has the structure:
adhesive properties are shown in table 1.
Comparative example 4
The process of example 1 was repeated at the indicated contents of the components, but without lowering the temperature in step one. Adhesive properties are shown in table 1.
Comparative example 5
The process of example 1 was repeated with the indicated amounts of the components, but the blocking agent added in step one was ethylene glycol ethyl ether. Adhesive properties are shown in table 1.
TABLE 1
As can be seen from table 1 above, the polyurethane emulsion adhesive of the present invention has high initial adhesion, fast crystallization speed, and high crystallinity.
Claims (5)
1. A preparation method of a polyurethane emulsion adhesive containing nano-cellulose whiskers is characterized by comprising the following steps:
the method comprises the following steps: under the protection of nitrogen, adding 1mol of polyhexamethylene adipate glycol and 2mol of toluene diisocyanate, stirring for 2-3 h at the temperature of 60-70 ℃, adding 100g of nanocellulose whisker, adding 2wt% of dibutyltin dilaurate, continuing stirring for 1-2 h at the temperature of 80-90 ℃, then reducing the temperature, adding 1mol of sealing agent, and continuing stirring for 2h to obtain a prepolymer A, wherein 2wt% is based on the sum of the polyhexamethylene adipate glycol and the toluene diisocyanate;
the structural formula of the prepolymer A is as follows:
step two: under the protection of dry nitrogen, adding 10mol of polyhexamethylene glycol adipate diol with the molecular weight of 4000 and 20mol of toluene diisocyanate into a reaction kettle, heating to 60 ℃, stirring for 2h, adding 2wt% of dibutyltin dilaurate, and continuously stirring for 2h to obtain a prepolymer B, wherein the 2wt% is based on the sum of the polyhexamethylene glycol adipate diol and the toluene diisocyanate;
step three: adding 5mol of dimethylolpropionic acid into the prepolymer B obtained in the step two, heating and stirring, finally adding 2mol of trimethylolpropane and 1mol of diethylene glycol, adjusting the system viscosity to 2000-4000 mPa.s by using acetone, stirring for 3h at the speed of 40r/min, cooling to 50 ℃, adding the prepolymer A obtained in the step one according to the mass ratio of the system to the prepolymer A of 1:1, and continuously stirring for 1h at the speed of 40r/min to obtain a polyurethane solution;
step four: and (3) adding the polyurethane solution obtained in the third step into deionized water at a mass ratio of 1:0.5 under stirring at 50r/min, stirring for 1h, and then carrying out reduced pressure distillation to remove the solvent acetone, thereby obtaining the aqueous polyurethane emulsion adhesive containing the nano-cellulose whiskers.
2. The polyurethane emulsion containing nanocellulose whiskers as claimed in claim 1The preparation method of the liquid adhesive is characterized in that the length-diameter ratio of the nano cellulose whiskers in the step one is 200, and the specific surface area is 200m2(ii)/g, the number of surface hydroxyl groups is 30.0OH/nm2。
3. The preparation method of the polyurethane emulsion adhesive containing the nano-cellulose whiskers, as claimed in claim 1, is characterized in that, in the first step, the temperature is reduced to 50 ℃, and the added blocking agent is acetophenone oxime.
4. The preparation method of the polyurethane emulsion adhesive containing the nano-cellulose whiskers as claimed in claim 1, wherein in the third step, dimethylolpropionic acid is added and then stirred at 60-70 ℃ for 1-2 h.
5. A polyurethane emulsion adhesive containing nano-cellulose whiskers prepared according to the method of any one of claims 1-4.
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| CN112707971B (en) * | 2019-10-24 | 2022-03-29 | 中国石油天然气股份有限公司 | Modified nano-cellulose crystal and preparation method thereof |
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| CN111531660B (en) * | 2020-05-09 | 2022-02-08 | 中国林业科学研究院木材工业研究所 | Low-formaldehyde impregnated bond paper facing artificial board and preparation method thereof |
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Effective date of registration: 20220105 Address after: 212221 xilaiqiao Town, Yangzhong City, Zhenjiang City, Jiangsu Province Patentee after: ZHENJIANG JIANGGUAN ELECTRICAL APPLIANCES CO.,LTD. Address before: 1 No. 211167 Jiangsu city of Nanjing province Jiangning Science Park Hongjing Road Patentee before: NANJING INSTITUTE OF TECHNOLOGY |