CN106928423B - High-temperature-cooking-resistant polyester polyurethane resin and preparation method thereof - Google Patents
High-temperature-cooking-resistant polyester polyurethane resin and preparation method thereof Download PDFInfo
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- CN106928423B CN106928423B CN201710314320.8A CN201710314320A CN106928423B CN 106928423 B CN106928423 B CN 106928423B CN 201710314320 A CN201710314320 A CN 201710314320A CN 106928423 B CN106928423 B CN 106928423B
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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
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/329—Hydroxyamines containing aromatic groups
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- 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
- C08G18/44—Polycarbonates
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- 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
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- 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
- C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
- C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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Abstract
A high-temperature-cooking-resistant polyester polyurethane resin and a preparation method thereof. The polyester polyurethane resin comprises the following components in parts by weight: 20-50 parts of polyester polyol, 4-10 parts of diisocyanate, 30-50 parts of ethyl acetate, 15-40 parts of isopropanol, 0.5-3 parts of amine chain extender and 0.18-0.3 part of alcamines blocking agent; wherein the weight average molecular weight of the polyester polyol is 1500-3500, and the acid value is 0.4-0.7mg KOH/g. The polyester type polyurethane resin provided by the invention has higher composite strength and excellent high-temperature cooking resistance.
Description
Technical Field
The invention belongs to the field of high molecular polymers, and particularly discloses a high-temperature-cooking-resistant polyester polyurethane resin and a preparation method thereof.
Background
Polyurethane (PU) is a short name for Polyurethane (Polyurethane) which is a high polymer containing a large number of carbamate groups (-NHCOO-) on the main chain, and is a high polymer mainly formed by polymerizing polyisocyanates such as diisocyanate and the like and low-molecular polymeric diols. The polymer material has excellent physical and chemical properties, is widely applied to various industries, is a multifunctional polymer material, and becomes an indispensable high polymer material in the social and economic development.
In addition, by changing the type of polyisocyanate and changing the structure, molecular weight, etc. of the polyol, the properties of the polyurethane material can be changed over a wide range. The polyurethane adhesive is an adhesive containing urethane group (-NHCOO-) and/or isocyanate group (-NCO-) in molecular chain. Polyurethane adhesives are one of the important varieties in synthetic adhesives due to superior performance, and are widely applied in national economy, for example, in ink printing.
With the rapid development of flexible packaging composite materials, people continuously have an enhanced environmental awareness on the flexible packaging composite materials, and the requirements on the printing safety and environmental protection of food flexible packaging composite materials are higher and higher. The traditional printing inks such as chlorinated polypropylene printing ink and polyamide printing ink mainly adopt toluene, butanone, cyclohexanone and the like as solvents, wherein the toluene has strong toxicity, the residual butanone has strong smell and certain toxicity, and the printing inks are easy to pollute air when in use and cause great harm to human health. In order to prevent various toxic and harmful substances from directly or indirectly damaging human bodies, a series of health and safety regulations are introduced by the nation to prohibit the use of benzene solvents for flexible packaging composite materials and strictly control the residual quantity of the solvents. In addition, with the progress of times and the improvement of life quality, the flexible packaging composite printing product not only requires environmental protection, but also needs higher composite strength to meet higher requirements of people for life, thereby promoting the continuous technical innovation of the flexible packaging composite printing industry, and developing and applying green and environment-friendly products.
For example, CN 104031467a discloses a preparation method of an environment-friendly solvent type polyurethane ink, which comprises the following steps: 1) adding maleic anhydride, adipic acid and methyl propylene glycol into a reaction kettle in N2Under protection, heating for reaction; adding stannous chloride, and continuing to react to obtain non-crystallized polyester polyol; 2) drying the non-crystalline polyester polyol prepared in the step 1), adding the dried non-crystalline polyester polyol into a reaction kettle, and dropwise adding diisocyanate into the reaction kettle for reaction; then dripping a catalyst, heating and continuing to react to obtain a polyurethane prepolymer; 3) diluting the polyurethane prepolymer with ethyl acetate until the mass fraction of the polyurethane prepolymer is 10-20%; adding chain extender and cross-linking agent, mixing, adding ethyl acetateAnd isopropanol to obtain the environment-friendly solvent type polyurethane ink. However, the polyurethane ink prepared by the method has insufficient high-temperature boiling resistance.
As is known, high-temperature cooking is an efficient and thorough sterilization process, is widely used for the sterilization treatment of meat, bean products, partial medical supplies and medical injection, and is gradually used for the sterilization treatment of cooked Chinese chestnuts, grain pulp beverages, infant fruit and vegetable paste and other foods and various packaging bags in recent years. Therefore, the adhesive used needs to be of high-temperature cooking resistant grade, generally considered to at least meet the cooking requirement of more than 121 ℃, and must have good bonding strength, high-temperature medium resistance and heat resistance after being compounded, and the most common adhesive at present is a two-component polyurethane adhesive; the temperature range of high-temperature steaming sterilization is generally between 121 ℃ and 135 ℃, and flexible packaging materials meeting the requirement of 145 ℃ ultra-high temperature sterilization are also researched at present. Although more high-temperature cooking cover films are produced and applied in the period from the birth of the high-temperature cooking bag to half a century now, the composite flexible packaging material meeting the cooking requirement of 121 ℃ is quite mature, but few mature products which really meet the requirement of more than 135 ℃ in the domestic market are available.
Generally, under high temperature and high humidity, the urethane group is very easy to hydrolyze and finally decompose, which causes a great reduction in adhesive strength, thereby affecting the use performance; this is the biggest bottleneck limiting its use in high temperature fields; then, how to improve the heat resistance of the polyurethane adhesive is also a critical technology.
CN 105131892a discloses a two-component polyurethane adhesive composition with chemical resistance and high temperature cooking resistance and a preparation method thereof, wherein the preparation method comprises the following steps: synthesizing polyester polyol, namely mixing multiple dibasic acids, multiple dihydric alcohols and a catalyst, and reacting for 8 to 20 hours at the temperature of between 130 and 250 ℃ to obtain the polyester polyol; the hydroxyl-terminated polyurethane prepolymer is synthesized by mixing the obtained polyester polyol, ethyl acetate, diisocyanate, catalyst and special auxiliary agent, and then carrying out chain extension reaction for 3-12 hours at 50-100 ℃ to obtain the hydroxyl-terminated polyurethane prepolymer, and after the hydroxyl-terminated polyurethane prepolymer is matched with a curing agent NCO component, the two-component polyurethane adhesive composition has good leveling property, high cohesive strength, high adhesive strength and low residual solvent. CN 104672421A discloses a preparation method of a composite ink binder polyurethane resin, which adopts a two-pot three-step method to prepare a polyurethane product, namely, firstly, a prepolymer is prepared from polyol and diisocyanate in a prepolymerization kettle, then the prepolymer is dripped into a chain extension kettle, and finally, an end-capping agent is added to cap. Wherein, in the step of preparing the prepolymer, a step of gradient temperature rise reaction is used for replacing the catalyst in the prior art. In addition, the invention also relates to the polyurethane resin prepared by the method and the composite ink for gravure printing comprising the polyurethane resin.
However, the polyurethane adhesive composition prepared by the above method is still to be further improved in the composite strength and the retort resistance when used for ink printing.
Disclosure of Invention
Therefore, one of the technical problems to be solved by the present invention is to provide a high temperature retort resistant polyester polyurethane resin. The polyester type polyurethane resin provided by the invention is solvent-free environment-friendly resin, has high composite strength and resists high-temperature cooking.
In order to achieve the purpose, the invention adopts the following technical means:
the high-temperature-cooking-resistant polyester polyurethane resin comprises the following components in parts by weight:
0.15-0.3 part of alcohol amine blocking agent;
wherein the polyester polyol has a weight average molecular weight of 1500-.
The polyester polyols are, for example, 22 parts, 26 parts, 29 parts, 32 parts, 36 parts, 38 parts, 41 parts, 44 parts, 47 parts, 49.5 parts, and the like.
Examples of the diisocyanate include 4.5 parts, 6 parts, 7 parts, 8 parts, 9 parts and the like.
Examples of the ethyl acetate include 32 parts, 36 parts, 38 parts, 41 parts, 44 parts, 47 parts, 49.5 parts, and the like.
Examples of the isopropyl alcohol include 17 parts, 19 parts, 22 parts, 26 parts, 29 parts, 32 parts, 36 parts, 38 parts, and the like.
Examples of the amine chain extender include 0.7 part, 0.9 part, 1.2 parts, 1.6 parts, 1.9 parts, 2.2 parts, 2.6 parts, and 2.9 parts.
Examples of the alkanolamine blocking agent include 0.17 part, 0.19 part, 0.21 part, 0.24 part, 0.27 part, and 0.29 part.
Preferably, the polyester polyurethane resin comprises the following components in parts by weight:
wherein the weight average molecular weight of the polyester polyol is 1500-3500, and the acid value is 0.2-0.8mg KOH/g.
The polyester polyurethane resin is obtained by using 3500 polyester polyol with the weight-average molecular weight of 1500-3500 and the acid value of 20-50mg KOH/g and diisocyanate as basic components and utilizing the synergistic effect of the two components and matching with an amine chain extender and an alcamines end-capping reagent, and has excellent high-temperature cooking resistance and high composite strength.
Preferably, the polyester polyol has a weight average molecular weight of 2000-2500 and an acid value of 0.4-0.6mg KOH/g.
Preferably, the polyester polyol is one or a mixture of two or more of aromatic polyester diol and polycarbonate diol.
Preferably, the aromatic polyester diol is obtained by reacting isophthalic acid with a diol.
Preferably, the diol is 2-isopropyl-1, 4-butanediol, 3-methyl-1, 5-pentanediol or 2, 4-dimethyl-1, 5-pentanediol.
The use of the polyester polyol described above can provide a resin with higher composite strength.
Preferably, the diisocyanate is one or a mixture of at least two of aliphatic diisocyanate and aromatic diisocyanate, preferably one or a mixture of at least two of dodecamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, 2, 4-toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, 3 '-dimethyl-4, 4-biphenyl diisocyanate or p-phenylene diisocyanate, and more preferably one or a mixture of at least two of dodecamethylene diisocyanate, xylylene diisocyanate and 3, 3' -dimethyl-4, 4-biphenyl diisocyanate.
Preferably, the amine chain extender may be ethylenediamine and/or N, N-dihydroxy (diisopropyl) aniline (HPA), preferably N, N-dihydroxy (diisopropyl) aniline.
Preferably, the alkanolamine blocking agent may be ethanolamine and/or propanolamine.
The raw material of the polyurethane may further contain various additives, and specific examples thereof include a phosphorus-containing flame retardant, an antioxidant, a heat stabilizer, an anti-hydrolysis agent, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, and the like. These various additives may be used alone or in combination of two or more.
The polyester polyurethane resin provided by the present invention may be prepared by methods known in the art or discovered in the future.
Preferably, the preparation method of the high temperature and boiling resistant polyester polyurethane resin comprises the following steps:
(1) reacting a polyester polyol and a diisocyanate under the following conditions: first raising the temperature to 80-100 ℃, such as 83 ℃, 86 ℃, 89 ℃, 92 ℃, 95 ℃, 98 ℃ and the like for 1-2 hours, such as 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours and the like, and then raising the temperature to 130-150 ℃, such as 133 ℃, 136 ℃, 139 ℃, 142 ℃, 145 ℃, 148 ℃ and the like for 0.5 hour or more, such as 0.7 hour, 0.9 hour, 1.2 hour, 1.5 hour, 1.9 hour, 2.3 hour, 2.8 hour and the like, preferably 1-2;
(2) and (2) adding other components into the product obtained in the step (1) to react to obtain the polyester type polyurethane resin.
Preferably, the temperature of the reaction in step (2) is 40-90 deg.C, such as 43 deg.C, 46 deg.C, 49 deg.C, 52 deg.C, 55 deg.C, 58 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 82 deg.C, 87 deg.C, preferably 60-80 deg.C; the reaction time is 1 hour or more, for example, 1.2 hours, 1.5 hours, 2.3 hours, 4 hours, 6 hours, etc., preferably 2 to 5 hours.
An object of the present invention is also to provide an ink comprising the polyester urethane resin according to the present invention.
The term "comprising" as used herein means that it may include, in addition to the components, other components which impart different properties to the thermoplastic polyurethane elastomer. In addition, the terms "comprising" and "including" as used herein may be replaced by the terms "comprising" or "consisting of … ….
The product provided by the invention has the following advantages: 1. controllable molecular weight and structure; 2. excellent adhesion; 3. good color development performance and alcohol ester solubility; 4. good high-temperature steaming and boiling resistance and weather resistance; 5. the ink prepared by the resin has excellent printing adaptability and can adapt to high, medium and low speed printing.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
Example 1
The high-temperature-cooking-resistant polyester polyurethane resin comprises the following components in parts by weight:
wherein the polyester polyol has a weight average molecular weight of 1500 and an acid value of 0.2mg KOH/g.
The polyester polyol is obtained by polymerizing isophthalic acid and 3-methyl-1, 5-pentanediol.
The diisocyanate is xylylene diisocyanate.
The amine chain extender is ethylenediamine.
The alcamines blocking agent is propanolamine.
Example 2
The high-temperature-cooking-resistant polyester polyurethane resin comprises the following components in parts by weight:
wherein the polyester polyol has a weight average molecular weight of 3500 and an acid value of 0.8mg KOH/g.
The polyester polyol is polycarbonate 2-isopropyl-1, 4 butanediol.
The diisocyanate is xylylene diisocyanate.
The amine chain extender is N, N-dihydroxy (diisopropyl) aniline.
The alcohol amine blocking agent is ethanolamine.
Example 3
The high-temperature-cooking-resistant polyester polyurethane resin comprises the following components in parts by weight:
wherein the polyester polyol has a weight average molecular weight of 2500 and an acid value of 0.4mg KOH/g.
The polyester polyol is obtained by polymerizing isophthalic acid and 2, 4-dimethyl-1, 5-pentanediol.
The diisocyanate is toluene diisocyanate.
The amine chain extender is ethylenediamine.
The alcamines blocking agent is propanolamine.
Example 4
The high-temperature-cooking-resistant polyester polyurethane resin comprises the following components in parts by weight:
wherein the polyester polyol has a weight average molecular weight of 3000 and an acid value of 0.5mg KOH/g.
The polyester polyol is polycarbonate 3-methyl-1, 5-pentanediol.
The diisocyanate is diphenylmethane diisocyanate.
The amine chain extender is N, N-dihydroxy (diisopropyl) aniline.
The alcamines blocking agent is propanolamine.
Example 5
The high-temperature-cooking-resistant polyester polyurethane resin comprises the following components in parts by weight:
wherein the polyester polyol has a weight average molecular weight of 2000 and an acid value of 0.6mg KOH/g.
The polyester polyol is polycarbonate 2-isopropyl-1, 4 butanediol.
The diisocyanate is diphenylmethane diisocyanate.
The amine chain extender is ethylenediamine.
The alcohol amine blocking agent is ethanolamine.
Example 6
The high-temperature-cooking-resistant polyester polyurethane resin comprises the following components in parts by weight:
wherein the polyester polyol has a weight average molecular weight of 3000 and an acid value of 0.3mg KOH/g.
The polyester polyol is obtained by polymerizing isophthalic acid and 2-isopropyl-1, 4-butanediol.
The diisocyanate is dodecamethylene diisocyanate.
The amine chain extender is N, N-dihydroxy (diisopropyl) aniline.
The alcamines blocking agent is propanolamine.
Comparative example 1
Same composition as example 4, except for the following differences:
wherein the polyester polyol has a weight average molecular weight of 4000 and an acid value of 0.3mg KOH/g.
Comparative example 2
Same composition as example 4, except for the following differences:
wherein the polyester polyol has a weight average molecular weight of 1000 and an acid value of 0.8mg KOH/g.
Comparative example 3
Same composition as example 4, except for the following differences:
the polyester polyol is polybutylene adipate.
Comparative example 4
Same composition as example 4, except for the following differences:
the diisocyanate is hexamethylene diisocyanate.
Performance testing
Inks prepared using the resins prepared in the above examples were tested for performance. The detection method is carried out as follows: the gravure plastic film is compounded with ink QB/T2024-. The results of the performance tests are shown in Table 1.
TABLE 1
And (3) composite strength determination: the PET composite PE is used as a composite structure, the adhesive of the resin is used, and the using amount of the adhesive is 2.3g/m2。
The samples prepared for performance testing were cooked in an autoclave at 135 ℃ for 45 minutes before the performance testing was performed, and the test results are shown in table 2.
TABLE 2
As can be seen from tables 1 and 2, the resins obtained in the examples of the present invention have excellent adhesion fastness, tinting strength, composite strength and blocking resistance, are free of solvents of the benzophenone type, and have very good properties that fully meet the standards after autoclaving. As can be seen from comparison of comparative examples 1 and 2 with example 4, use of polyester polyol having a weight average molecular weight and an acid value that are too low or too high significantly affects the adhesion fastness, tinting strength, composite strength and blocking resistance of the resin. As seen from a comparison of comparative example 3 with example 4, the absence of the preferred polyester polyols of the present invention results in a significant reduction in the properties of the resulting resin. As can be seen from a comparison of comparative example 4 with example 4, the choice of diisocyanate also has a major effect on the properties of the resulting resin. The invention selects the proper polyester polyol to be matched with the diisocyanate for use, so that the prepared resin has very good comprehensive performance.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
The applicant states that on the basis of the above-mentioned examples, the specific content point values of the components in the above-mentioned examples are combined with the technical solutions in the summary of the invention, so as to generate a new numerical range, which is also one of the described ranges of the present invention, and the present application does not list these numerical ranges again for the sake of brevity.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (7)
1. The high-temperature-cooking-resistant polyester polyurethane resin is characterized by comprising the following components in parts by weight:
wherein the weight average molecular weight of the polyester polyol is 1500-3500, and the acid value is 0.4-0.7mg KOH/g;
the polyester polyol is one or a mixture of more than two of aromatic polyester dihydric alcohol and polycarbonate dihydric alcohol; the aromatic polyester dihydric alcohol is obtained by reacting isophthalic acid with dihydric alcohol;
wherein the dihydric alcohol is one of 2-isopropyl-1, 4-butanediol, 3-methyl-1, 5-pentanediol or 2, 4-dimethyl-1, 5-pentanediol;
the diisocyanate is one of dodecamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate.
2. The polyester polyurethane resin according to claim 1, comprising the following components in parts by weight:
wherein the weight average molecular weight of the polyester polyol is 1500-3500, and the acid value is 0.4-0.7mg KOH/g.
3. The polyester polyurethane resin according to claim 1 or 2, wherein the polyester polyol has a weight average molecular weight of 2000-2500 and an acid value of 0.6mg KOH/g.
4. The polyester polyurethane resin according to claim 1 or 2, wherein the amine chain extender is ethylenediamine and/or N, N-dihydroxy (diisopropyl) aniline; the alcoholamines blocking agent is ethanolamine and/or propanolamine.
5. A method for preparing the polyester polyurethane resin according to any one of claims 1 to 4, comprising the steps of:
(1) reacting a polyester polyol and a diisocyanate under the following conditions: firstly heating to 80-100 ℃ for reaction for 1-2 hours, and then heating to 130-150 ℃ for reaction for more than 0.5 hour;
(2) and (2) adding other components into the product obtained in the step (1) to react to obtain the polyester type polyurethane resin.
6. The method according to claim 5, wherein the temperature of the reaction in the step (2) is 40 to 90 ℃; the reaction time is 1 hour or more.
7. An ink comprising the polyester polyurethane resin according to any one of claims 1 to 4.
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| CN112538149B (en) * | 2019-09-23 | 2022-07-12 | 万华化学集团股份有限公司 | Preparation process of casting polyurethane elastomer |
| CN112321787A (en) * | 2020-11-03 | 2021-02-05 | 黄山中泽新材料有限公司 | Preparation method and application of polyurethane binder for food packaging extrusion composite ink |
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