CN112375535A - Plastic-plastic composite polyurethane adhesive and preparation method thereof - Google Patents
Plastic-plastic composite polyurethane adhesive 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
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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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
- C08G18/48—Polyethers
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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
- C08G18/6629—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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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
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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Abstract
The invention provides a plastic-plastic composite polyurethane adhesive and a preparation method thereof, wherein the prepared adhesive is a bi-component adhesive and comprises a component A and a component B; the component A comprises isocyanate-terminated prepolymer; the component B is prepared from 5-20 parts by weight of 3-functionality polyether polyol, 50-90 parts by weight of polyester polyol, 5-15 parts by weight of micromolecular dihydric alcohol, 0-15 parts by weight of hexamethylene diisocyanate, 1-5 parts by weight of silane coupling agent and 1-3 parts by weight of heat stabilizer. The prepared adhesive shows excellent flexibility and very good peel strength when being used in plastic composite materials, and has excellent boiling resistance.
Description
Technical Field
The invention relates to a polyurethane adhesive technology, in particular to a plastic-plastic composite polyurethane adhesive and a preparation method thereof.
Background
The polyurethane adhesive is an adhesive containing carbamate (-NHCOO-) or isocyanate (-NCO) in a molecular chain, shows high activity and polarity, and has excellent chemical bonding force with substrates containing active hydrogen, such as porous materials of foam, plastic, wood, leather, fabric, paper, ceramic and the like, and materials with smooth surfaces of metal, glass, rubber, plastic and the like.
The polyurethane adhesive can be divided into a single-component polyurethane adhesive and a double-component polyurethane adhesive, and the single-component polyurethane adhesive has the defects of poor later heat resistance, large smell and the like. The bi-component polyurethane adhesive has good initial bonding performance and final bonding performance. However, with the gradual improvement and continuous perfection of food packaging and sterilization modes in the food industry, the demand on high-temperature cooking resistant flexible packaging plastic-plastic composite products is continuously increased, so that the research and development of the bi-component polyurethane adhesive with good flexibility, high peel strength and water cooking resistance is of great significance.
Disclosure of Invention
In order to solve the above problems, the first aspect of the present invention provides a plastic-plastic composite polyurethane adhesive, which is a two-component adhesive, comprising a component a and a component B;
the component A comprises an isocyanate-terminated prepolymer;
the component B is prepared from the following raw materials in parts by weight: 5-20 parts of 3-functionality polyether polyol, 50-90 parts of polyester polyol, 5-15 parts of small molecular dihydric alcohol, 0-15 parts of hexamethylene diisocyanate, 1-5 parts of a silane coupling agent and 1-3 parts of a heat stabilizer;
when in use, the component A and the component B are mixed according to the weight ratio of 1: (2-3) mixing uniformly.
As a preferred technical scheme, the preparation raw materials of the isocyanate-terminated prepolymer comprise: 25-50 parts of polyether polyol and 50-60 parts of isocyanate.
As a preferable technical scheme, the polyether polyol is a mixture of polyether polyols with the number average molecular weights of 300-500, 800-1200 and 1800-2200, and the weight ratio is (1-2): (2-3): (1-2).
As a preferable technical scheme, the hydroxyl value of the polyether polyol with the molecular weight of 300-500 is 250-320 mgKOH/g; the hydroxyl value of the polyether polyol with the molecular weight of 800-1200 is 100-130 mgKOH/g; the hydroxyl value of the polyether polyol with the molecular weight of 1800-2200 is 50-65 mgKOH/g.
As a preferable technical scheme, the isocyanate is a mixture of 4, 4 '-diphenylmethane diisocyanate and 2, 4' -diphenylmethane diisocyanate, and the weight ratio is (4-6): 1.
as a preferable technical scheme, the polyester polyol is a mixture of polyester polyol with the molecular weight of 1000-1500 and castor oil-based polyol.
As a preferable technical scheme, the hydroxyl value of the castor oil-based polyol is 40-50 mgKOH/g.
As a preferable technical scheme, the weight ratio of the polyester polyol with the molecular weight of 1000-1500 to the castor oil-based polyol is (3-5): 1.
as a preferable technical scheme, the micromolecular dihydric alcohol is one or a mixture of a plurality of diethylene glycol, 1, 4-butanediol and 1, 6-hexanediol.
The second aspect of the invention provides a preparation method of a plastic-plastic composite polyurethane adhesive, which comprises the following steps,
(1) preparation of component A: according to the formula amount, putting polyether polyol into a flask, heating, stirring, vacuumizing and dehydrating until no obvious bubbles are generated in the system, and then completing dehydration to obtain dehydrated polyether polyol; and adding isocyanate into the four-neck flask according to the formula amount, dropwise adding dehydrated polyether polyol, introducing nitrogen for protection, carrying out heat preservation reaction for 2 hours, and cooling to obtain the isocyanate-terminated prepolymer.
(2) Preparation of component B: according to the formula, uniformly mixing 3-functionality polyether polyol, polyester polyol, micromolecular dihydric alcohol, hexamethylene diisocyanate, a silane coupling agent and a heat stabilizer to obtain the component B.
Has the advantages that:
1. the weight ratio of the polyether polyols with the molecular weights of 300-500, 800-1200 and 1800-2200 is (1-2): (2-3): (1-2), NCO in the synthesized isocyanate prepolymer and OH in the component B can be crosslinked and cured to form macromolecules, and the macromolecules have a chain segment with strong cohesive force and a flexible chain segment, so that the peel strength and viscoelasticity of the adhesive are improved, and the adhesive has better cohesiveness and boiling resistance.
2. The isocyanate is a mixture of 4, 4 '-diphenylmethane diisocyanate and 2, 4' -diphenylmethane diisocyanate, and the weight ratio is (4-6): 1; reduces the self-polymerization of isocyanate, and improves the transparency and preparation efficiency of the isocyanate-terminated prepolymer.
3. The polyester polyol is a mixture of polyester polyol with the molecular weight of 1000-1500 and castor oil-based polyol, so that the thermal stability, hydrolysis resistance and boiling resistance of the adhesive are further improved.
4. The weight ratio of the polyester polyol with the molecular weight of 1000-1500 to the castor oil-based polyol is (3-5): 1, the strength and the flexibility of the adhesive film are improved.
5. The hydroxyl value of the polyether polyol with the molecular weight of 300-500 is 255-312 mgKOH/g; the hydroxyl value of the polyether polyol with the molecular weight of 800-1200 is 102-125 mgKOH/g; the hydroxyl value of the polyether polyol with the molecular weight of 1800-2200 is 51-62 mgKOH/g; the reaction for preparing the isocyanate-terminated prepolymer is facilitated to be carried out stably.
Detailed Description
The invention will be further understood by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definition provided in the present disclosure, the definition of the term provided in the present disclosure controls.
As used herein, a feature that does not define a singular or plural form is also intended to include a plural form of the feature unless the context clearly indicates otherwise. It will be further understood that the term "prepared from …," as used herein, is synonymous with "comprising," including, "comprising," "having," "including," and/or "containing," when used in this specification means that the recited composition, step, method, article, or device is present, but does not preclude the presence or addition of one or more other compositions, steps, methods, articles, or devices. Furthermore, the use of "preferred," "preferably," "more preferred," etc., when describing embodiments of the present invention, is meant to refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. In addition, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
In order to solve the above problems, the first aspect of the present invention provides a plastic-plastic composite polyurethane adhesive, which is a two-component adhesive, comprising a component a and a component B;
the component A comprises an isocyanate-terminated prepolymer; the preparation raw materials of the isocyanate-terminated prepolymer comprise, by weight, 25-50 parts of polyether polyol and 50-60 parts of isocyanate;
the polyether polyol is selected from one or a mixture of polyethylene glycol (PEG), polypropylene glycol (PPG) and polytetrahydrofuran; in some preferred embodiments, in order to improve the safety and environmental protection of the adhesive, the polyether polyol is selected from PPG, and in addition, the addition of PPG also improves the flexibility and transparency of the adhesive, and improves the application of the adhesive in the field of flexible packaging, which may be because the PPG molecular chain contains a side methyl group, and this special molecular structure can destroy the linear symmetry of the macromolecular structure formed after the component a and the component B are cross-linked and cured, thereby improving the flexibility of the adhesive, and the transparency and boiling resistance of the adhesive.
In order to improve the flexibility of the adhesive, in some preferred embodiments, the polyether polyol is a mixture of polyether polyols with number average molecular weights of 300-500, 800-1200, 1800-2200.
In some more preferred embodiments, the weight ratio of the polyether polyols having molecular weights of 300-500, 800-1200, 1800-2200 is (1-2): (2-3): (1-2), NCO in the synthesized isocyanate prepolymer and OH in the component B can be crosslinked and cured to form macromolecules, and the macromolecules have a chain segment with strong cohesive force and a flexible chain segment, so that the peel strength and viscoelasticity of the adhesive are improved, and the adhesive has better cohesiveness and boiling resistance. If the content of the polyether polyol with the molecular weight of 300-500 is too high, more closely arranged urethane bonds generated by combination with isocyanate are increased, so that the acting force between hydrogen bonds and polar bonds in molecules is increased, the viscosity of the isocyanate-terminated prepolymer is too high, and the full mixing of the component A and the component B and the subsequent coating process are influenced. If the content of polyether polyol with the molecular weight of 1800-2200 is too high, the proportion of soft segments in the isocyanate-terminated prepolymer is increased, the content of rigid groups is reduced, the acting force of hydrogen bonds is weakened, the bonding effect of the adhesive and a matrix is finally reduced, and the peeling strength is reduced.
In some more preferred embodiments, the polyether polyol having a molecular weight of 300 to 500 has a hydroxyl value of 255 to 312 mgKOH/g; the hydroxyl value of the polyether polyol with the molecular weight of 800-1200 is 102-125 mgKOH/g; the hydroxyl value of the polyether polyol with the molecular weight of 1800-2200 is 51-62 mgKOH/g; the method is favorable for the stable reaction of preparing the isocyanate-terminated prepolymer, and the polyether polyols with different hydroxyl values can continuously and stably provide hydroxyl groups for the isocyanate in the prepolymerization process, so that the reaction process can be stably carried out at a certain speed, the performance cannot be influenced by too violent reaction, and the efficiency cannot be influenced by too slow reaction.
The isocyanate is selected from one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI) and polymethylene polyphenyl isocyanate (PAPI).
In order to reduce the volatilization of the isocyanate during the preparation of the isocyanate-terminated prepolymer, thereby reducing the environmental hazard and waste of raw materials, in some preferred embodiments, the isocyanate is MDI.
In order to improve the transparency and preparation efficiency of the isocyanate-terminated prepolymer, in some more preferred embodiments, the MDI is a mixture of 4, 4 '-diphenylmethane diisocyanate and 2, 4' -diphenylmethane diisocyanate in a weight ratio of (4-6): 1; if the content of the 4, 4' -diphenylmethane diisocyanate is too high, the NCO group of the 4, 4' -diphenylmethane diisocyanate has higher activity, so that the 4, 4' -diphenylmethane diisocyanate is easy to self-polymerize after reacting with polyether polyol in a system to a certain degree in the process of preparing the isocyanate-terminated prepolymer, the viscosity of the prepolymer is increased, and the transparency is poor. On the contrary, if the content of 4, 4' -diphenylmethane diisocyanate is too low, the time of the prepolymerization reaction is increased, thereby reducing the preparation efficiency of the isocyanate-terminated prepolymer.
The component B is prepared from the following raw materials, by weight, 5-20 parts of 3-functionality polyether polyol, 50-90 parts of polyester polyol, 5-15 parts of micromolecule dihydric alcohol, 0-15 parts of hexamethylene diisocyanate, 1-5 parts of a silane coupling agent and 1-3 parts of a heat stabilizer.
In order to reduce NCO dissociation in the adhesive and reduce pollution to packaged goods, in some preferred embodiments, the hydroxyl value of the 3-functionality polyether polyol is 100-200 mgKOH/g, such as polyether polyols available from Heian petrochemical plants of Jiangsu province, and having the types HSH-206 and HSH-210.
In order to further improve the thermal stability, hydrolysis resistance and boiling resistance of the adhesive, in some preferred embodiments, the polyester polyol is a mixture of a polyester polyol with a molecular weight of 1000-1500 and a castor oil-based polyol.
In order to improve the softness and extensibility of the adhesive, in some preferred embodiments, the hydroxyl value of the castor oil-based polyol is 40 to 50 mgKOH/g.
In some more preferred embodiments, the weight ratio of the polyester polyol having a molecular weight of 1000 to 1500 to the castor oil-based polyol is (3 to 5): 1, the strength and flexibility of the adhesive film formed by mixing and curing the component A and the component B are improved. If the content of the castor oil-based polyol is too high, the internal crosslinking degree of the polyester polyol is increased, so that the movement between polymer chains formed by the polyester polyol and the terminal isocyanate prepolymer of the component A is hindered, and an adhesive film becomes brittle and poor in flexibility. If the castor oil based polyol content is too low, the thermal stability and water resistance of the adhesive will be reduced.
In some preferred embodiments, the small-molecule diol is selected from one or more of diethylene glycol, 1, 4-butanediol and 1, 6-hexanediol, so that the crosslinking density and the hard segment content of the cured polymers of the component A and the component B can be improved, the bulk strength of the adhesive is increased, and the peeling strength and the temperature resistance of the plastic-plastic composite adhesive are improved.
A certain amount of coupling agent is added into the component B, so that the curing rate of the adhesive can be effectively accelerated, and the curing time is shortened. In some preferred embodiments, the coupling agent is selected from one or more of N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane and gamma-glycidoxypropyltrimethoxysilane, so that the dispersion uniformity of the components in the component B can be improved, and the bonding durability of the adhesive can be improved.
In order to improve the heat resistance of the adhesive, the heat stabilizer is selected from any one or a combination of several of an antioxidant 245, an antioxidant 264, an antioxidant 1010, an antioxidant 1035, an antioxidant 1076, an antioxidant 1098, an antioxidant 1135 and an antioxidant 168.
The second aspect of the invention provides a preparation method of a plastic-plastic composite polyurethane adhesive, which comprises the following steps;
(1) preparation of a middle-end isocyanate prepolymer in the component A:
according to the formula amount, putting polyether polyol into a three-neck flask provided with a stirrer and a thermometer for heating, starting stirring, heating and vacuumizing, and dehydrating at 110-120 ℃ until no obvious bubbles are generated in the system, thus obtaining dehydrated polyether polyol. And then adding isocyanate according to the formula amount into a four-neck flask provided with a stirrer, a condenser pipe, a constant-pressure dropping funnel and a thermometer, dropping the dehydrated polyether glycol at 35-45 ℃ for 1-1.5 h, introducing nitrogen for protection, keeping the temperature for reaction for 2h, and cooling to obtain the isocyanate-terminated prepolymer.
The NCO content of the isocyanate-terminated prepolymer is determined according to the standard HG/T2409-92, and the isocyanate-terminated prepolymer with the NCO content of 16-20 percent is preferred.
(2) Preparation of component B: according to the formula, uniformly mixing 3-functionality polyether polyol, polyester polyol, micromolecular dihydric alcohol, hexamethylene diisocyanate, a silane coupling agent and a heat stabilizer to obtain the component B.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
The technical solution of the present invention is described in detail by the following examples, but the scope of the present invention is not limited to the examples.
Example 1
Embodiment 1 provides a plastic-plastic composite polyurethane adhesive, which is a bi-component adhesive and comprises a component A and a component B;
the component A comprises an isocyanate-terminated prepolymer; the preparation raw materials of the isocyanate-terminated prepolymer comprise 35 parts by weight of polyether polyol and 55 parts by weight of isocyanate;
the polyether polyol is a mixture of PPG-400 (purchased from Hainan petrochemical plant of Jiangsu province, molecular weight is 360-440, hydroxyl value is 255-312 mg KOH/g), PPG-1000 (purchased from Hainan petrochemical plant of Jiangsu province, molecular weight is 900-1100, hydroxyl value is 102-125 mg KOH/g), PPG-2000 (purchased from Hainan petrochemical plant of Jiangsu province, molecular weight is 1800-2200, hydroxyl value is 51-62 mg KOH/g), and the weight ratio is 1: 2: 1.
the isocyanate is a mixture of 4, 4 '-diphenylmethane diisocyanate and 2, 4' -diphenylmethane diisocyanate, and the weight ratio is 5: 1.
the component B is prepared from the following raw materials in parts by weight: 10 parts of 3-functionality polyether polyol, 65 parts of polyester polyol, 10 parts of micromolecular dihydric alcohol, 8 parts of hexamethylene diisocyanate, 3 parts of silane coupling agent and 2 parts of heat stabilizer.
The hydroxyl value of the 3-functionality polyether polyol is 178-197 mg KOH/g, and the 3-functionality polyether polyol is purchased from Haian petrochemical plants in Jiangsu province and has the model of HSH-206.
The polyester polyol is a mixture of polyester polyol (purchased from Shanghai Yu chemical Co., Ltd., molecular weight of 1000 and type of L3025) with molecular weight of 1000-1500 and castor oil-based polyol (purchased from Ito oil-making Co., Ltd., hydroxyl value of 45mg KOH/g and type of Uric PH-5001) in a weight ratio of 4: 1.
the micromolecular dihydric alcohol is diethylene glycol.
The coupling agent is gamma-aminopropyl triethoxysilane.
The heat stabilizer is an antioxidant 245.
The second aspect of the present embodiment provides a method for preparing a plastic-plastic composite polyurethane adhesive, including the following steps;
(1) preparation of a middle-end isocyanate prepolymer in the component A:
according to the formula amount, placing PPG-400, PPG-1000 and PPG-2000 in a three-neck flask with a stirrer and a thermometer for heating, starting stirring, heating and vacuumizing, and dehydrating at 115 ℃ until no obvious bubbles are generated in the system, namely, the dehydration is finished, thereby obtaining the dehydrated polyether polyol. And then adding 4, 4 '-diphenylmethane diisocyanate and 2, 4' -diphenylmethane diisocyanate according to the formula amount into a four-neck flask provided with a stirrer, a condenser pipe, a constant-pressure dropping funnel and a thermometer, dropwise adding the polyether glycol subjected to dehydration treatment in advance at 40 ℃ for 1-1.5 h, introducing nitrogen for protection, carrying out heat preservation reaction for 2h, and cooling to obtain the isocyanate-terminated prepolymer.
(2) Preparation of component B: according to the formula, uniformly mixing 3-functionality polyether polyol, polyester polyol, micromolecular dihydric alcohol, hexamethylene diisocyanate, a silane coupling agent and a heat stabilizer to obtain the component B.
When in use, the component A and the component B are mixed according to the weight ratio of 1: (2-3) mixing uniformly.
Example 2
Similar to example 1, a plastic composite polyurethane adhesive, a preparation method and a preparation method thereof are provided, but the preparation raw material of the component B comprises the following components in parts by weight: 10 parts of 3-functionality polyether polyol, 50 parts of polyester polyol, 10 parts of micromolecular dihydric alcohol, 8 parts of hexamethylene diisocyanate, 3 parts of a silane coupling agent and 2 parts of a heat stabilizer.
Example 3
Similar to example 1, a plastic composite polyurethane adhesive, a preparation method and a preparation method thereof are provided, but the preparation raw material of the component B comprises the following components in parts by weight: 10 parts of 3-functionality polyether polyol, 90 parts of polyester polyol, 10 parts of micromolecular dihydric alcohol, 8 parts of hexamethylene diisocyanate, 3 parts of a silane coupling agent and 2 parts of a heat stabilizer.
Comparative example 1
Similar to example 1, a plastic composite polyurethane adhesive, a preparation method and a preparation method thereof are provided, but the preparation raw material of the component B comprises the following components in parts by weight: 0 part of 3-functionality polyether polyol, 65 parts of polyester polyol, 10 parts of micromolecular dihydric alcohol, 8 parts of hexamethylene diisocyanate, 3 parts of silane coupling agent and 2 parts of heat stabilizer.
Comparative example 2
Similar to example 1, a plastic composite polyurethane adhesive, a preparation method and a preparation method thereof are provided, but the preparation raw material of the component B comprises the following components in parts by weight: 10 parts of 3-functionality polyether polyol, 65 parts of polyester polyol, 0 part of micromolecular dihydric alcohol, 8 parts of hexamethylene diisocyanate, 3 parts of silane coupling agent and 2 parts of heat stabilizer.
Comparative example 3
Similar to example 1, a plastic composite polyurethane adhesive, a preparation method and a preparation method thereof are provided, but the preparation raw material of the component B comprises the following components in parts by weight: 10 parts of 3-functionality polyether polyol, 65 parts of polyester polyol, 10 parts of micromolecular dihydric alcohol, 8 parts of hexamethylene diisocyanate, 0 part of silane coupling agent and 2 parts of heat stabilizer.
Comparative example 4
Similar to example 1, a plastic-plastic composite polyurethane adhesive, a preparation method and a preparation method thereof are provided, but in the raw materials for preparing the isocyanate-terminated prepolymer, the polyether polyol is PPG-1000, which is purchased from Haian petrochemical plants of Jiangsu province, has a molecular weight of 900-1100 and a hydroxyl value of 102-125 mg KOH/g.
Comparative example 5
Similar to example 1, a plastic-plastic composite polyurethane adhesive, a preparation method and a preparation method thereof are provided, but in the raw materials for preparing the isocyanate-terminated prepolymer, the isocyanate is TDI.
Comparative example 6
A plastic composite polyurethane adhesive, a preparation method and a preparation method thereof are provided similarly to example 1, but the weight ratio of the 4, 4 '-diphenylmethane diisocyanate to the 2, 4' -diphenylmethane diisocyanate is 8: 1.
comparative example 7
Similar to the embodiment 1, the plastic-plastic composite polyurethane adhesive, the preparation method and the preparation method thereof are provided, but the polyester polyol is the polyester polyol with the molecular weight of 1000-1500.
Comparative example 8
Similar to the embodiment 1, the plastic composite polyurethane adhesive, the preparation method and the preparation method thereof are provided, but the weight ratio of the polyester polyol with the molecular weight of 1000-1500 to the castor oil-based polyol is 2: 1.
comparative example 9
Similar to the embodiment 1, the plastic-plastic composite polyurethane adhesive and the preparation method and preparation method thereof are provided, wherein the weight ratio of polyether polyol with the molecular weight of 300-500, 800-1200 and 1800-2200 is 1: 2: 3.
evaluation of Performance
The adhesive prepared in the examples 1-3 and the comparative examples 1-9, namely the component A and the component B, are uniformly mixed according to the weight ratio of 1:2 and then coated on a PET film, wherein the gluing amount is about 2g/m2Then placing the PET/PE composite film into a 42 ℃ oven for baking for 10s, taking out the PET/PE composite film, laminating the PET/PE composite film with the PE film, performing hot pressing at 40 ℃ for 10s under 0.2Mpa to obtain a PET/PE composite film, curing the PET/PE composite film for 48h at room temperature, and testing various performance technical indexes of the PET/PE composite film according to the following test methods:
1. and (3) testing the peel strength: the peel strength of the synthesized adhesive-coated PET/PE composite film was measured according to GB/T2791-1995, and the results are reported in Table 1.
2. Boiling resistance test: the PET/PE composite film is boiled in boiling water at 100 ℃ for 30min, and the PET/PE bonding layer is observed to be complete without foaming, delamination and degumming phenomena, which shows that the hot melt adhesive has good boiling resistance and is recorded as good, otherwise, the hot melt adhesive is recorded as poor, and the results are recorded in Table 1.
TABLE 1
The embodiments 1-3 and the comparative examples 1-9 show that the plastic-plastic composite polyurethane adhesive and the preparation method thereof provided by the invention have excellent flexibility and very good peel strength and excellent boiling resistance when used in plastic-plastic composite materials.
Finally, it should be understood that the above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The plastic composite polyurethane adhesive is characterized in that: the adhesive is a bi-component adhesive and comprises a component A and a component B;
the component A comprises an isocyanate-terminated prepolymer;
the component B is prepared from the raw materials of, by weight, 5-20 parts of 3-functionality polyether polyol, 50-90 parts of polyester polyol, 5-15 parts of micromolecular dihydric alcohol, 0-15 parts of hexamethylene diisocyanate, 1-5 parts of a silane coupling agent and 1-3 parts of a heat stabilizer;
when in use, the component A and the component B are mixed according to the weight ratio of 1: (2-3) mixing uniformly.
2. The plastic-plastic composite polyurethane adhesive as claimed in claim 1, wherein: the preparation raw materials of the isocyanate-terminated prepolymer comprise: 25-50 parts of polyether polyol and 50-60 parts of isocyanate.
3. The plastic-plastic composite polyurethane adhesive as claimed in claim 2, wherein: the polyether polyol is a mixture of polyether polyols with the number average molecular weights of 300-500, 800-1200 and 1800-2200, and the weight ratio is (1-2): (2-3): (1-2).
4. The plastic-plastic composite polyurethane adhesive as claimed in claim 3, wherein: the hydroxyl value of the polyether polyol with the molecular weight of 300-500 is 250-320 mgKOH/g; the hydroxyl value of the polyether polyol with the molecular weight of 800-1200 is 100-130 mgKOH/g; the hydroxyl value of the polyether polyol with the molecular weight of 1800-2200 is 50-65 mgKOH/g.
5. The plastic-plastic composite polyurethane adhesive as claimed in claim 2, wherein: the isocyanate is a mixture of 4, 4 '-diphenylmethane diisocyanate and 2, 4' -diphenylmethane diisocyanate, and the weight ratio is (4-6): 1.
6. the plastic-plastic composite polyurethane adhesive as claimed in claim 1, wherein: the polyester polyol is a mixture of polyester polyol with the molecular weight of 1000-1500 and castor oil-based polyol.
7. The plastic-plastic composite polyurethane adhesive as claimed in claim 6, wherein: the hydroxyl value of the castor oil-based polyol is 40-50 mgKOH/g.
8. The plastic-plastic composite polyurethane adhesive as claimed in claim 7, wherein: the weight ratio of the polyester polyol with the molecular weight of 1000-1500 to the castor oil-based polyol is (3-5): 1.
9. the plastic-plastic composite polyurethane adhesive as claimed in claim 1, wherein: the micromolecular dihydric alcohol is one or a mixture of diethylene glycol, 1, 4-butanediol and 1, 6-hexanediol.
10. A method for preparing the plastic composite polyurethane adhesive according to any one of claims 1 to 9, comprising the following steps,
(1) preparation of component A: according to the formula amount, putting polyether polyol into a flask, heating, stirring, vacuumizing and dehydrating until no obvious bubbles are generated in the system, and then completing dehydration to obtain dehydrated polyether polyol; and adding isocyanate into the four-neck flask according to the formula amount, dropwise adding dehydrated polyether polyol, introducing nitrogen for protection, carrying out heat preservation reaction for 2 hours, and cooling to obtain the isocyanate-terminated prepolymer.
(2) Preparation of component B: according to the formula, uniformly mixing 3-functionality polyether polyol, polyester polyol, micromolecular dihydric alcohol, hexamethylene diisocyanate, a silane coupling agent and a heat stabilizer to obtain the component B.
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| CN114591710A (en) * | 2021-12-29 | 2022-06-07 | 张家港爱科思汽车配件有限公司 | Bi-component PU structural adhesive and preparation method thereof |
| CN115181529A (en) * | 2022-08-01 | 2022-10-14 | 普分新材料研究(上海)有限公司 | Antibacterial polyurethane hot melt adhesive suitable for garment fabric and preparation method thereof |
| CN115505362A (en) * | 2022-10-31 | 2022-12-23 | 北京高盟新材料股份有限公司 | Solvent-free polyurethane adhesive for composite low-surface-energy film and preparation method thereof |
| CN115537173A (en) * | 2022-02-28 | 2022-12-30 | 安吉巨树新材料科技有限公司 | Washable high-viscosity single-component adhesive and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114591710A (en) * | 2021-12-29 | 2022-06-07 | 张家港爱科思汽车配件有限公司 | Bi-component PU structural adhesive and preparation method thereof |
| CN115537173A (en) * | 2022-02-28 | 2022-12-30 | 安吉巨树新材料科技有限公司 | Washable high-viscosity single-component adhesive and preparation method thereof |
| CN115537173B (en) * | 2022-02-28 | 2023-11-10 | 安吉巨树新材料科技有限公司 | Washable high-viscosity single-component adhesive and preparation method thereof |
| CN115181529A (en) * | 2022-08-01 | 2022-10-14 | 普分新材料研究(上海)有限公司 | Antibacterial polyurethane hot melt adhesive suitable for garment fabric and preparation method thereof |
| CN115505362A (en) * | 2022-10-31 | 2022-12-23 | 北京高盟新材料股份有限公司 | Solvent-free polyurethane adhesive for composite low-surface-energy film and preparation method thereof |
| CN115505362B (en) * | 2022-10-31 | 2023-11-17 | 北京高盟新材料股份有限公司 | Solvent-free polyurethane adhesive for composite low-surface-energy film and preparation method thereof |
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