CN115536806B - Production process of aqueous polyurethane emulsion of ultrahigh-elongation coating film - Google Patents

Production process of aqueous polyurethane emulsion of ultrahigh-elongation coating film Download PDF

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CN115536806B
CN115536806B CN202211186300.4A CN202211186300A CN115536806B CN 115536806 B CN115536806 B CN 115536806B CN 202211186300 A CN202211186300 A CN 202211186300A CN 115536806 B CN115536806 B CN 115536806B
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parts
chain extender
aqueous polyurethane
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coating film
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CN115536806A (en
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姜大炜
黄斌
冯燕
顾小敏
钮珊珊
成忠权
郭琦
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Jiangsu second normal university
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Abstract

The invention discloses an aqueous polyurethane emulsion of an ultra-high tensile rate coating film, which comprises 0-24 parts of polyether polyol 3010E, 0-20 parts of polyether polyol PTMG-2000, 0-20 parts of polyester polyol P2010, 1090 14-31 parts of polycarbonate polyol C, 4.2 parts of small molecule chain extender, 4.4 parts of hydrophilic chain extender and 37.62 parts of isocyanate IPDI; the invention provides a water-based polyurethane emulsion coating film which can replace polyethylene, polyvinyl chloride and the like and is used for express packaging materials, so as to solve the problem of white pollution caused by the difficult-to-degrade plastic packaging bag; the coating film obtained by the process has ultrahigh stretching rate, the stretched length can reach more than 19 times of the original length, and the use of polyethylene, polyvinyl chloride and other packaging bags can be reduced to a great extent; meanwhile, because ester bonds and amide bonds exist in the aqueous polyurethane polymer chain, the aqueous polyurethane polymer chain can be degraded step by step under the condition of proper alkaline after being recovered, so that the generation of white pollution is eliminated, and harmful substances to the environment are avoided.

Description

Production process of aqueous polyurethane emulsion of ultrahigh-elongation coating film
Technical Field
The invention belongs to the field of synthesis of aqueous polyurethane emulsion, and particularly relates to aqueous polyurethane emulsion of a coating film with an ultrahigh stretching rate and a production process thereof.
Background
Polyurethane is an abbreviation for polyurethane. Is a high molecular compound, and is characterized in that repeated carbamate groups (-NHCOO-) are arranged in the molecular structure of a polymer chain. The polyurethane is a polymer material with wide application after being invented, can be made into products with different forms, and is a universal polymer which can be cut.
The aqueous polyurethane is prepared by performing polycondensation reaction on isocyanate, dihydric alcohol and the like to generate a prepolymer with-NCO at both ends, and then embedding diamine containing hydrophilic acid groups on a polyurethane molecular chain as a chain extender; depending on the number of functional groups of the starting materials used in the reaction, linear or steric structures can be produced. Because hydrophilic groups are introduced into the prepolymer, the prepolymer has certain degree of hydrophilicity, and then is emulsified by salifying and dispersed into water to prepare the aqueous polyurethane, which is also called polyurethane water dispersion. The water PU has the characteristics of innocuity, incombustibility, explosion-proof, environmental protection and the like.
In recent years, with the continuous enhancement of environmental awareness of people, compared with the traditional solvent-based polyurethane, the waterborne polyurethane has the characteristics of no pollution, low emission of organic volatile matters and the like, and is more and more focused by students and becomes a research hot spot. The aqueous polyurethane has unique molecular structure and aggregation state, so that the adhesive film has the characteristics of excellent mechanical property, wear resistance, adhesive force and the like, and is widely applied to the fields of clothing, shoe industry, leather bags, household articles, furniture, automobiles and transportation facilities, textile auxiliary agents, papermaking auxiliary agents, paint, adhesive and the like. The solvent such as DMF, toluene and MEK is not used in the synthesis of the aqueous polyurethane, so the aqueous polyurethane is pollution-free; the aqueous polyurethane emulsion has the advantages of non-combustibility, safety, environmental protection, no toxicity, no pollution and the like, and can meet the environmental protection requirement of no VOC emission, so that the aqueous polyurethane emulsion is more and more important; the modern industry developed countries have adopted aqueous polyurethane resins to replace solvent polyurethanes for production.
Nowadays, with the rapid development of economy, garbage is increased, especially plastic garbage. The garbage is stable in property, difficult to degrade and scattered everywhere, and commonly called white pollution. One of these sources is the plastic packaging bag of the outer layer of the express box. The common express package outer layer packaging material at present is Polyethylene (PE) or polyvinyl chloride (PVC). The existing treatment method for white pollution is recycling and reutilizing, and the other method is incineration, for example, power generation and the like as energy incineration; however, in the incineration process, the carcinogenic dioxin is inevitably released into the atmosphere, and the environmental pollution is aggravated. Meanwhile, the carbon emission content is increased by incineration power generation, and the requirements of sustainable development are not met.
Disclosure of Invention
In order to solve the problems, the invention discloses a water-based polyurethane emulsion coating film which can replace polyethylene, polyvinyl chloride and other packaging materials so as to solve the problem of white pollution caused by the plastic packaging bag which is difficult to degrade, and the coating film has ultrahigh stretching rate.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
and (3) reacting polymer polyol (polyether polyol, polyester polyol and polycarbonate polyol) micromolecular chain extender, hydrophilic chain extender and isocyanate by adopting a prepolymer method, adding a neutralizing agent to form salt after reaching theoretical NCO% value, and finally adding deionized water and a post chain extender to stir and disperse to obtain the aqueous polyurethane emulsion with the high-elongation coating film.
The method specifically comprises the following steps:
(1) Mixing and stirring polyether polyol 3010E, polyether polyol PTMG-2000, polyester polyol P2010 and polycarbonate polyol C1090, and carrying out primary temperature rise reaction; after adding isocyanate, carrying out a secondary heating reaction; then adding a small molecular chain extender, and carrying out three-time heating reaction; then adding a hydrophilic chain extender, reacting for 30 minutes, and then carrying out four-time heating reaction; obtaining a prepolymer;
(2) And when the prepolymer reaches the theoretical NCO% value, cooling, adding acetone for dilution, adding a neutralizing agent for salifying, and finally adding deionized water and a rear chain extender for stirring and dispersing to obtain the aqueous polyurethane emulsion with the high-elongation coating film.
In the preparation process of the aqueous polyurethane emulsion, the raw materials used in the preparation process are as follows in parts by weight: 0-24 parts of polyether polyol 3010E, 0-20 parts of polyether polyol PTMG-2000, 0-20 parts of polyester polyol P2010, 1090 14-31 parts of polycarbonate polyol C, 4.2 parts of small molecule chain extender, 4.4 parts of hydrophilic chain extender and 37.62 parts of isocyanate; 30 parts of acetone, 3.3 parts of neutralizer, 174-192 parts of deionized water and 2.6-3 parts of post chain extender.
Further, the isocyanate is isophorone diisocyanate (IPDI).
Further, the small molecule chain extender is 1, 4-Butanediol (BDO).
Further, the hydrophilic chain extender is dimethylolpropionic acid (DMPA).
Further, the neutralizing agent is triethylamine.
Further, the rear chain extender is hydrazine hydrate.
Further, in the step (1), the temperature of the primary heating reaction is 60-65 ℃ and the time is 30-40 minutes; the temperature of the secondary heating reaction is 70-75 ℃ and the time is 30-40 minutes; the temperature of the three heating reactions is 80-85 ℃ and the time is 20-30 minutes; the temperature of the four heating reactions is 90-95 ℃ and the time is 30-35 minutes.
The beneficial effects of the invention are as follows:
the aqueous polyurethane emulsion is obtained by combining the proportion of the raw materials and the production process, the prepared coating film has ultrahigh stretching rate, the stretched length can reach more than 19 times of the original length, and the use of packaging bags such as polyethylene, polyvinyl chloride and the like can be reduced to a great extent. Meanwhile, because ester bonds and amide bonds exist in the aqueous polyurethane polymer chain, the aqueous polyurethane polymer chain can be degraded step by step under the condition of proper alkaline after being recovered, so that the white pollution is eliminated, and harmful substances are avoided.
Detailed Description
The present invention will be further elucidated with reference to the following embodiments, which should be understood as merely illustrative of the invention and not as limiting the scope of the invention.
Example 1
(1) 24 g polyether polyol 3010E,20 g polyether polyol PTMG2000, 31 g polycarbonate polyol C1090 are weighed into a four-necked flask, stirring is started, heating is carried out to 60 ℃ and preserving heat for 30 minutes, then 37.62 g IPDI is added, heating is carried out to 70 ℃, the reaction is continued for about 30 minutes, 4.2 g BDO is added, heating is carried out to 80 ℃ and preserving heat for 20 minutes; then adding 4.4 g of DMPA, reacting for 30 minutes, heating to 90-95 ℃, and continuing to react for 30-35 minutes to obtain a prepolymer;
(2) Sampling and titration are carried out in the reaction process to know the NCO value, after the prepolymer reaches the NCO% theoretical value of 2.82%, acetone 30 g is added for dilution when the prepolymer is cooled to 60 ℃, the prepolymer is cooled to 30 ℃, a neutralizing agent triethylamine 3.3 g is added for salifying for 15 minutes, and finally a mixture of deionized water 191 g and 2.6 g hydrazine hydrate is added for stirring and dispersing for 30 minutes, so that the aqueous polyurethane emulsion is obtained.
Example 2
(1) 24 g polyether polyol 3010E,20 g polyether polyol PTMG2000, 20 g polyester polyol P2010, 14 g polycarbonate polyol C1090 are weighed into a four-necked flask, stirring is started, heating is carried out to 60 ℃ and heat preservation is carried out for 30 minutes, then 37.62 g IPDI is added, heating is carried out to 70 ℃, the reaction is continued for about 30 minutes, 4.2 g BDO is added, heating is carried out to 80 ℃ and heat preservation is carried out for 20 minutes; then adding 4.4 g of DMPA, reacting for 30 minutes, heating to 90-95 ℃, and continuing to react for 30-35 minutes to obtain a prepolymer;
(2) Sampling and titration are carried out in the reaction process to know the NCO value, after the NCO% theoretical value reaches 3.23%, acetone 30 and g are added for dilution when the prepolymer is cooled to 60 ℃, the prepolymer is cooled to 30 ℃, a neutralizing agent triethylamine 3.3 and g is added for salifying for 15 minutes, and finally a mixture of deionized water 192 g and 3.0 and g hydrazine hydrate is added for stirring and dispersing for 30 minutes, so that the aqueous polyurethane emulsion is obtained.
Example 3
(1) 24 g polyether polyol 3010E,20 g of polyester polyol P2010, 31 g polycarbonate polyol C1090 are weighed into a four-necked flask, stirring is started, heating is carried out to 60 ℃ and heat preservation is carried out for 30 minutes, then 37.62 g of IPDI is added, heating is carried out to 70 ℃, the reaction is continued for about 30 minutes, 4.2 g of BDO is added, heating is carried out to 80 ℃ and heat preservation is carried out for 20 minutes; then adding 4.4 g of DMPA, reacting for 30 minutes, heating to 90-95 ℃, and continuing to react for 30-35 minutes to obtain a prepolymer;
(2) Sampling and titration are carried out in the reaction process to know the NCO value, after the prepolymer reaches the NCO% theoretical value of 2.82%, acetone 30 g is added for dilution when the prepolymer is cooled to 60 ℃, the prepolymer is cooled to 30 ℃, a neutralizing agent triethylamine 3.3 g is added for salifying for 15 minutes, and finally a mixture of deionized water 191 g and 2.6 g hydrazine hydrate is added for stirring and dispersing for 30 minutes, so that the aqueous polyurethane emulsion is obtained.
Example 4
(1) Weighing 20 g polyether polyol PTMG2000, 20 g polyester polyol P2010, 24 g polycarbonate polyol C1090 in a four-necked flask, starting stirring, heating to 60 ℃ and preserving heat for 30 minutes, then adding 37.62 g of IPDI, heating to 70 ℃, continuing to react for about 30 minutes, adding 4.2 g of BDO, heating to 80 ℃ and preserving heat for 20 minutes; then adding 4.4 g of DMPA, reacting for 30 minutes, heating to 90-95 ℃, and continuing to react for 30-35 minutes to obtain a prepolymer;
(2) Sampling and titration are carried out in the reaction process to know the NCO value, after the prepolymer reaches the NCO% theoretical value of 3.58%, cooling, adding acetone 30 g for dilution when the prepolymer is cooled to 60 ℃, cooling to 30 ℃, adding a neutralizing agent of triethylamine 3.3 g, salifying for 15 minutes, finally adding a mixture of deionized water 174 g and 3 g hydrazine hydrate, stirring and dispersing for 30 minutes, and obtaining the aqueous polyurethane emulsion.
Comparative examples
(1) 70.5 g g polyether polyol 3010E and 51 g polyether polyol PTMG2000 are weighed into a four-necked flask, stirring is started, heating is carried out to 60 ℃ and heat preservation is carried out for 30 minutes, then 37.62 g IPDI is added, heating is carried out to 70 ℃, the reaction is continued for about 30 minutes, 4.2 g BDO is added, and heating is carried out to 80 ℃ and heat preservation is carried out for 20 minutes; then adding 4.4 g of DMPA, reacting for 30 minutes, heating to 90-95 ℃, and continuing to react for 30-35 minutes to obtain a prepolymer;
(2) Sampling and titration are carried out in the reaction process to know the NCO value, after the prepolymer reaches the NCO% theoretical value of 2.82%, acetone 30 g is added for dilution when the prepolymer is cooled to 60 ℃, the prepolymer is cooled to 30 ℃, a neutralizing agent triethylamine 3.3 g is added for salifying for 15 minutes, and finally a mixture of deionized water 191 g and 2.6 g hydrazine hydrate is added for stirring and dispersing for 30 minutes, so that the aqueous polyurethane emulsion is obtained.
Performance test:
the aqueous polyurethane emulsion prepared in example 1-example 4 was coated on mirror centrifugal paper and dried in a blowing oven at 120℃to obtain a polyurethane coating film (test film thickness: 0.09 mm). After 48 hours, the film profile was cut into dumbbell shapes and tensile tested.
A tensile force test is carried out by using a universal material tester (a CMT6104 electronic universal tester controlled by a Metts microcomputer) (the running speed of the instrument is 400 mm/min; the thickness of a dumbbell-shaped test film is 0.09 mm); the test results show that the waterborne polyurethane coating films prepared by the process have ultrahigh stretching rate, and the obtained values show that the films are still not broken when the range is exceeded, and the stretching rate test data are shown in table 1.
Table 1 elongation at break test data
Film degradation experiment
The aqueous polyurethane coating films prepared in example 1-example 4 were taken in 4 beakers, 5% NaOH solution 30 mL was added, stirring was started and heated to 80 ℃. After 10 hours, the heating and stirring were stopped, cooled to room temperature, the whole film disappeared, and waxy solid precipitated and small amounts of fine film-like fragments appeared in the beaker. The polyurethane coating film can be degraded, and can replace polyethylene, polyvinyl chloride and other packaging materials, so that the purpose of reducing white pollution is achieved.
It should be noted that the foregoing merely illustrates the technical idea of the present invention and is not intended to limit the scope of the present invention, and that a person skilled in the art may make several improvements and modifications without departing from the principles of the present invention, which fall within the scope of the claims of the present invention.

Claims (2)

1. The aqueous polyurethane emulsion of the coating film with the ultra-high tensile rate is characterized by comprising the following raw materials in parts by weight: 24 parts of polyether polyol 3010E, 24 parts of polyether polyol PTMG-2000 20 parts of polyester polyol P2010 0-20 parts, 25-31 parts of polycarbonate polyol C1090 14-31 parts of small molecule chain extender 4.2 parts of hydrophilic chain extender 4.4 parts of isocyanate 37.62 parts, 30 parts of acetone, 3.3 parts of neutralizer, 174-192 parts of deionized water and 2.6-3 parts of rear chain extender;
the preparation method of the aqueous polyurethane emulsion of the coating film with the ultra-high tensile rate comprises the following steps:
(1) Mixing and stirring polyether polyol 3010E, polyether polyol PTMG-2000, polyester polyol P2010 and polycarbonate polyol C1090 in parts by weight, and performing primary temperature rise reaction; after adding isocyanate, carrying out a secondary heating reaction; then adding a small molecular chain extender, and carrying out three-time heating reaction; then adding a hydrophilic chain extender, reacting for 30 minutes, and then carrying out four-time heating reaction; obtaining a prepolymer;
(2) Cooling, diluting with acetone, adding a neutralizing agent to form salt, and finally adding deionized water and a rear chain extender, and stirring and dispersing to obtain the aqueous polyurethane emulsion with the high-stretching-rate coating film;
in the step (1), the temperature of the primary heating reaction is 60-65 ℃ and the time is 30-40 minutes; the temperature of the secondary heating reaction is 70-75 ℃ and the time is 30-40 minutes; the temperature of the three heating reactions is 80-85 ℃ and the time is 20-30 minutes; the temperature of the four heating reactions is 90-95 ℃ and the time is 30-35 minutes;
the isocyanate is isophorone diisocyanate;
the small molecule chain extender is 1, 4-butanediol;
the hydrophilic chain extender is dimethylolpropionic acid;
the rear chain extender is hydrazine hydrate.
2. The aqueous polyurethane emulsion of ultra-high elongation coated film according to claim 1, wherein the neutralizing agent is triethylamine.
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JP2016027073A (en) * 2013-11-07 2016-02-18 三菱化学株式会社 Polycarbonate diol, and polyurethane and urethane (meth)acrylate using the same
CN107759764A (en) * 2017-11-07 2018-03-06 江苏第二师范学院 The production technology of silicon dioxide carried high-strength water-based polyaminoester emulsion
WO2020105569A1 (en) * 2018-11-21 2020-05-28 三洋化成工業株式会社 Aqueous composite resin dispersion and method for producing aqueous composite resin dispersion
CN114381191A (en) * 2022-01-17 2022-04-22 江苏第二师范学院 Hydroxyl silicone oil modified waterborne polyurethane coating with high tensile strength and high water resistance coating film

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JP2016027073A (en) * 2013-11-07 2016-02-18 三菱化学株式会社 Polycarbonate diol, and polyurethane and urethane (meth)acrylate using the same
CN104893537A (en) * 2015-04-20 2015-09-09 江苏第二师范学院 Production process of waterborne polyurethane coating material having high tension force coating film
CN107759764A (en) * 2017-11-07 2018-03-06 江苏第二师范学院 The production technology of silicon dioxide carried high-strength water-based polyaminoester emulsion
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