CN115537171A - Low-temperature-resistant polyurethane composite adhesive and preparation method thereof - Google Patents

Low-temperature-resistant polyurethane composite adhesive and preparation method thereof Download PDF

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CN115537171A
CN115537171A CN202211182879.7A CN202211182879A CN115537171A CN 115537171 A CN115537171 A CN 115537171A CN 202211182879 A CN202211182879 A CN 202211182879A CN 115537171 A CN115537171 A CN 115537171A
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sampling
acid
resistant polyurethane
test
acid value
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吕少波
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Jiangsu Huada New Material Co ltd
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Jiangsu Huada New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • 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
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
    • 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
    • C08G18/65—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
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The application relates to the technical field of adhesives, in particular to a low-temperature-resistant polyurethane composite adhesive which comprises the following components in parts by weight: 20-40 parts of aromatic polybasic acid; 20-40 parts of polyol; 5-8 parts of aliphatic polybasic acid; 9-15 parts of polyisocyanate; 20-40 parts of a solvent; 0.03-0.06 part of catalyst; 0.1-1 part of cross-linking agent; 0.05 to 0.2 portion of terminator; the polyol comprises a component A, and the component A is selected from one or more of hydroquinone diisopropyl ether and 2,2' - [1,4-phenylene bis (oxy-2,1-ethanediyloxy) ] diethanol. The low-temperature-resistant polyurethane composite adhesive has the advantages of improving the fluidity of polyurethane at a low temperature and improving the flexibility of the polyurethane after curing at the low temperature.

Description

Low-temperature-resistant polyurethane composite adhesive and preparation method thereof
Technical Field
The application relates to the technical field of adhesives, in particular to a low-temperature-resistant polyurethane composite adhesive and a preparation method thereof.
Background
With the development of industry, the application market of the adhesive is more and more extensive, and the variety of the adhesive is also more and more. Among them, polyurethane adhesives have excellent flexibility, water resistance and solvent resistance, and are widely used in the fields of construction, automobiles, aerospace and the like, and become one of the indispensable important materials in many fields.
The polyurethane adhesive is an adhesive containing urethane groups (-NHCOO-) or isocyanate groups (-NCO) in a molecular chain. Because the polyurethane molecular chain contains isocyanate group and carbamate group with strong polarity, the polyurethane adhesive can show high activity and polarity in use, and has excellent chemical bonding force with materials containing active hydrogen, such as foam, plastic, wood, leather, fabric, paper, ceramic, metal, glass, rubber and the like.
The main chain of polyurethane molecule is block copolymer composed of flexible chain segment and rigid chain segment alternatively, the soft segment is polyol with polyester or polyether relatively high molecular weight, which provides toughness, elasticity and low temperature resistance of the composite adhesive, and the hard segment is composed of diisocyanate and diamine or diol with small relative molecular weight, which contributes to rigidity, strength and heat resistance of the composite adhesive.
However, the common polyurethane adhesive is easy to freeze in a low-temperature environment, so that the flowability is poor, the adhesive is difficult to prepare in use, and the construction is difficult or even impossible; meanwhile, the common polyurethane adhesive is brittle after being cured in a low-temperature environment, the physical properties are reduced, and the application of the polyurethane adhesive is greatly limited.
In view of this, it is necessary to develop a polyurethane laminating adhesive having good fluidity at low temperature and good flexibility after curing at low temperature.
Disclosure of Invention
In order to improve the fluidity of polyurethane at low temperature and the flexibility of the polyurethane after curing at low temperature, the application provides a low-temperature-resistant polyurethane composite adhesive and a preparation method thereof.
The application provides a low temperature resistant polyurethane composite adhesive adopts following technical scheme:
in a first aspect, the application provides a low temperature resistant polyurethane composite adhesive, which adopts the following technical scheme:
the low-temperature-resistant polyurethane composite adhesive comprises the following components in parts by weight:
20-40 parts of aromatic polybasic acid;
20-40 parts of polyol;
5-8 parts of aliphatic polybasic acid;
9-15 parts of polyisocyanate;
20-40 parts of a solvent;
0.03-0.06 part of catalyst;
0.1-1 part of a crosslinking agent;
0.05 to 0.2 portion of terminator;
the polyol comprises a component A, and the component A is selected from one or more of hydroquinone diisopropyl ether and 2,2' - [1,4-phenylene bis (oxy-2,1-ethanediyloxy) ] diethanol.
By adopting the technical scheme, hydroquinone diisopropyl alcohol ether and 2,2'- [1,4-phenylene bis (oxy-2,1-ethanediyloxy) ] diethanol can both form a flexible chain segment of a polyurethane system, and hydroquinone diisopropyl alcohol ether and 2,2' - [1,4-phenylene bis (oxy-2,1-ethanediyloxy) ] diethanol contain ether bonds which are easy to rotate, so that the flexibility of the molecular chain can be improved, and the low-temperature flexibility of the prepared low-temperature resistant polyurethane composite adhesive can be improved. Meanwhile, benzene rings exist in hydroquinone diisopropyl ether and 2,2' - [1,4-phenylene bis (oxy-2,1-ethanediyloxy) ] diethanol, and can improve the strength, toughness and low temperature resistance of the prepared low temperature resistant polyurethane composite adhesive; in addition, due to the existence of benzene rings in the hydroquinone diisopropyl alcohol ether and 2,2' - [1,4-phenylene bis (oxy-2,1-ethanediyloxy) ] diethanol, the hydroquinone diisopropyl alcohol ether and 2,2' - [1,4-phenylene bis (oxy-2,1-ethanediyloxy) ] diethanol can maintain good rotational flexibility, and the overall strength of the hydroquinone diisopropyl alcohol ether chain and 2,2' - [1,4-phenylene bis (oxy-2,1-ethanediyloxy) ] diethanol chain, so that the prepared low temperature resistant polyurethane composite gel has good flexibility and high strength after curing.
The ether bond in the hydroquinone diisopropyl ether is far away from the benzene ring, is less influenced by the benzene ring, has lower activity, and can improve the hydrolysis resistance of the prepared low-temperature-resistant polyurethane composite adhesive after curing by using the hydroquinone diisopropyl ether, thereby prolonging the service life of the prepared low-temperature-resistant polyurethane composite adhesive after curing; meanwhile, the length of the integral hydroquinone diisopropyl ether is longer, the mutual drag effect at two ends of the hydroquinone diisopropyl ether molecule is reduced, and the molecular chain is more flexible, so that the flexibility of the prepared low-temperature resistant polyurethane composite adhesive after curing can be improved.
2,2'- [1,4-phenylenebis (oxy-2,1-ethylenedioxy) ] diethanol molecule contains four ether bonds, so that 2,2' - [1,4-phenylenebis (oxy-2,1-ethylenedioxy) ] diethanol molecular chain has higher rotational flexibility, and the flexibility of the prepared low temperature resistant polyurethane composite gel after curing can be greatly improved.
In a specific embodiment, the solvent is selected from one or more of dimethyl carbonate, dimethyl formamide and ethyl acetate.
By adopting the technical scheme, the dimethyl carbonate, the dimethyl formamide, the butanone and the ethyl acetate have lower melting points, so that the prepared low-temperature-resistant polyurethane composite adhesive can keep better fluidity at low temperature.
In a specific embodiment, the aliphatic polybasic acid is selected from one or more of adipic acid, sebacic acid and succinic acid.
By adopting the technical scheme, adipic acid, sebacic acid and succinic acid can form a flexible chain segment of a polyurethane system, so that the low-temperature resistance and the cured flexibility of the prepared low-temperature-resistant polyurethane composite adhesive are improved.
In a specific possible embodiment, the polyol further comprises a B component, and the B component is selected from one or more of diethylene glycol, ethylene glycol, triethylene glycol, neopentyl glycol, hexanediol and butanediol.
By adopting the technical scheme, the component B and the component A are compounded for use, so that the low-temperature resistance of the prepared low-temperature-resistant polyurethane composite adhesive can be improved.
In a specific possible embodiment, the polyisocyanate comprises one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI).
In a specific embodiment, the aromatic polybasic acid is selected from one or more of terephthalic acid, phthalic anhydride and isophthalic acid.
In a specific possible embodiment, the catalyst is bismuth neodecanoate.
By adopting the technical scheme, the bismuth neodecanoate catalyst is safe and nontoxic, and accords with the concept of environmental protection.
In a specific embodiment, the cross-linking agent is selected from one or more of Trimethylolpropane (TMP) and glycerol.
By adopting the technical scheme, the trimethylolpropane has good hydrolytic resistance, oxidation resistance stability and alkali resistance, and is favorable for improving the stability of the low-temperature-resistant polyurethane composite adhesive after curing.
In a second aspect, the application provides a preparation method of a low temperature resistant polyurethane composite adhesive, which adopts the following technical scheme:
a preparation method of low-temperature-resistant polyurethane composite adhesive comprises the following steps:
(1) Adding 70-85 wt% of aromatic polybasic acid, 75 wt% of component A and component B into a reaction kettle, heating to 140-150 ℃, after reaction water is discharged, gradually discharging the water generated by the reaction, heating to 5 ℃ every 10min, gradually heating to 225 ℃, and then preserving heat;
(2) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified; after the requirement is met, firstly keeping the pressure for 1 to 2 hours under 0.4 to 0.6 standard atmospheric pressure, and then keeping the pressure for 2 to 3 hours under 300 to 1000 pa;
(3) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sampling test is qualified; cooling to 50-60 ℃ after the requirement is met, and pressing into a glue reaction kettle;
(4) Adding aliphatic polybasic acid, residual aromatic polybasic acid and residual component B into a reaction kettle, heating to 140-150 ℃, gradually discharging water generated by the reaction after reaction water is discharged, heating to 5 ℃ every 20min, gradually heating to 225 ℃, and then preserving heat;
(5) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified; after the requirement is met, keeping the pressure for 1 to 2 hours under 0.4 to 0.6 standard atmospheric pressure, and then keeping the pressure for 2 to 3 hours under 300 to 1000 pa;
(6) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sampling test is qualified, cooling to 50-60 ℃ after the requirement is met, and pressing into a glue reaction kettle;
(7) Adding partial solvent, cross-linking agent and catalyst into the glue reaction kettle at 80-85 ℃ to react for 2-3 h;
(8) Adding a terminating agent and the residual solvent, sampling to measure the solid content and the viscosity, and discharging after the requirements are met to obtain the low-temperature-resistant polyurethane composite adhesive.
By adopting the technical scheme, the preparation method is simple and easy to implement, does not need difficult preparation conditions, is easy to operate, and the prepared low-temperature-resistant polyurethane composite adhesive has good fluidity and flexibility at low temperature.
In a specific embodiment, the sample from step (8) has a solids content of 65% to 66% and a viscosity of 150 to 160 pas (25 ℃).
In summary, the present application has the following beneficial effects:
1. hydroquinone diisopropyl alcohol ether and 2,2' - [1,4-phenylene bis (oxy-2,1-ethanediyloxy) ] diethanol contain easily rotatable ether bonds, and can increase the flexibility of molecular chains, so that the low-temperature flexibility of the prepared low-temperature resistant polyurethane composite adhesive can be improved.
2. Dimethyl carbonate, dimethyl formamide, butanone and ethyl acetate all have lower melting points, so that the prepared low-temperature-resistant polyurethane composite adhesive can keep better fluidity at low temperature.
Detailed Description
The present application will be described in further detail with reference to examples.
Raw materials
In the relevant starting materials used in the preparations and examples:
Figure BDA0003867529460000041
Figure BDA0003867529460000051
examples
Example 1
The low-temperature-resistant polyurethane composite adhesive is prepared from the following raw materials:
50g of terephthalic acid, 210g of phthalic anhydride, 50g of hydroquinone diisopropanol ether, 100g of triethylene glycol, 50g of diethylene glycol, 30g of adipic acid, 30g of Toluene Diisocyanate (TDI), 80g of diphenylmethane diisocyanate (MDI), 260g of dimethyl carbonate, 40g of dimethylformamide, 40g of ethyl acetate, 0.5g of bismuth laurate, 5g of Trimethylolpropane (TMP) and 1g of phosphoric acid.
The preparation method of the low-temperature-resistant polyurethane composite adhesive comprises the following steps:
1. adding 50g of terephthalic acid, 150g of phthalic anhydride, 50g of hydroquinone diisopropyl ether, 62.5g of triethylene glycol and 50g of diethylene glycol into a reaction kettle, heating to 140 ℃, gradually discharging water generated by the reaction after reaction water is discharged, heating to 5 ℃ every 10min, gradually heating to 225 ℃, and then preserving heat;
(2) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified, keeping the pressure at 0.5 standard atmosphere for 1h, then vacuumizing, and keeping the pressure at 500Pa for 2.2h; in this example, the acid value was measured by sampling and found to be 23.5mgKOH/g;
(3) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sampling test is qualified, then cooling to 55 ℃, and pressing into a glue reaction kettle; in this example, the acid value was measured by sampling and was 0.4mgK0H/g, and the hydroxyl value was measured to be 56.3mgK0H/g;
(4) Adding 60g of phthalic anhydride, 30g of adipic acid and 37.5g of triethylene glycol into a reaction kettle, heating to 140 ℃, gradually discharging water generated by the reaction after reaction water is discharged, heating to 5 ℃ every 20min, gradually heating to 225 ℃, and then preserving heat;
(5) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified, keeping the pressure at 0.5 standard atmosphere for 1h, then vacuumizing, and keeping the pressure at 500Pa for 2.2h; in this example, the acid value was measured by sampling and found to be 23.8mgKOH/g;
(6) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sampling test is qualified, then cooling to 55 ℃, and pressing into a glue reaction kettle; in this example, the acid value was measured by sampling and was 0.3mgK0H/g, and the hydroxyl value was measured to be 55.4mgK0H/g;
(7) Adding 30g of TDI, 80g of MDI, 130g of dimethyl carbonate, 40g of dimethylformamide, 40g of ethyl acetate, 0.5g of bismuth laurate and 5g of TMP into a glue reaction kettle, and reacting for 2.2h at 80 ℃;
(8) Adding 1g of phosphoric acid and 130g of dimethyl carbonate into a glue reaction kettle, sampling to measure the solid content and the viscosity, wherein the solid content is 65-66% when the sample is qualified, the viscosity is 150-160 pas (25 ℃), and discharging to obtain the low-temperature-resistant polyurethane composite glue. The sample taken in this example showed a solids content of 65.5% and a viscosity of 155 pas (25 ℃).
Examples 2 to 9
Examples 2 to 9 are the same as example 1, except that the hydroquinone diisopropanol ether and 2,2' - [1,4-phenylenebis (oxy-2,1-ethylenedioxy) ] diethanol content are different, as specified in table 1:
TABLE 1 contents of some components of examples 2 to 9
Figure BDA0003867529460000061
Figure BDA0003867529460000071
Example 10
Example 10 is the same as example 2 except that 0.005g of antioxidant 168 was also added to the glue pot for reaction in step (7).
Example 11
A low-temperature-resistant polyurethane composite adhesive is prepared from the following raw materials:
60g of terephthalic acid, 100g of phthalic anhydride, 40g of isophthalic acid, 60g of hydroquinone diisopropanol ether, 2' - [1,4-phenylene bis (oxy-2,1-ethanediyloxy) ] diethanol 90g, 150g of triethylene glycol, 30g of succinic acid, 30g of Toluene Diisocyanate (TDI), 80g of diphenylmethane diisocyanate (MDI), 260g of dimethyl carbonate, 40g of dimethylformamide, 40g of ethyl acetate, 0.5g of bismuth laurate, 5g of Trimethylolpropane (TMP) and 1g of phosphoric acid.
The preparation method of the low-temperature-resistant polyurethane composite adhesive comprises the following steps:
(1) Adding 20g of terephthalic acid, 100g of phthalic anhydride, 20g of isophthalic acid, 60g of hydroquinone diisopropyl ether, 2,2' - [1,4-phenylenebis (oxy-2,1-ethanediyloxy) ] diethanol 90g and triethylene glycol 112.5g into a reaction kettle, heating to 140 ℃, gradually discharging water generated by the reaction after reaction water is discharged, heating to 5 ℃ every 10min, gradually heating to 225 ℃ and then preserving heat;
(2) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified, keeping the pressure at 0.5 standard atmosphere for 1h, then vacuumizing, and keeping the pressure at 500Pa for 2.2h; in this example, the acid value was measured by sampling and was 17.6mgKOH/g;
(3) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sample is qualified in the sampling test, then cooling to 55 ℃, and pressing into a glue reaction kettle; in this example, the acid value was measured by sampling and found to be 0.2mgK0H/g, and the hydroxyl value was measured to be 54.8mgK0H/g;
(4) Adding 40g of terephthalic acid, 20g of isophthalic acid, 30g of succinic acid and 37.5g of triethylene glycol into a reaction kettle, heating to 140 ℃, gradually discharging water generated by the reaction after the reaction is discharged, heating to 5 ℃ every 20min, gradually heating to 225 ℃, and then preserving heat;
(5) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified, keeping the pressure at 0.5 standard atmosphere for 1h, then vacuumizing, and keeping the pressure at 500Pa for 2.2h; in this example, the acid value was measured by sampling and found to be 19.6mgKOH/g;
(6) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sampling test is qualified, then cooling to 55 ℃, and pressing into a glue reaction kettle; in this example, the acid value was measured to be 0.4mgK0H/g and the hydroxyl value was measured to be 54.7mgK0H/g;
(7) Adding 30g of TDI, 80g of MDI, 130g of dimethyl carbonate, 40g of dimethylformamide, 40g of ethyl acetate, 0.5g of bismuth laurate and 5g of TMP into a glue reaction kettle, and reacting for 2.2h at 80 ℃;
(8) Adding 1g of phosphoric acid and 130g of dimethyl carbonate into a glue reaction kettle, sampling to measure the solid content and the viscosity, wherein the solid content is 65-66% when the sample is qualified, the viscosity is 150-160 pas (25 ℃), and discharging to obtain the low-temperature-resistant polyurethane composite glue. The sampling test in this example gave a solids content of 65.2% and a viscosity of 151 pas (25 ℃ C.).
Example 12
The low-temperature-resistant polyurethane composite adhesive is prepared from the following raw materials:
60g of terephthalic acid, 160g of phthalic anhydride, 40g of isophthalic acid, 90g of hydroquinone diisopropoxide ether 60g, 2' - [1,4-phenylene bis (oxy-2,1-ethanediyloxy) ] diethanol, 100g of triethylene glycol, 50g of neopentyl glycol, 30g of succinic acid, 30g of Toluene Diisocyanate (TDI), 80g of diphenylmethane diisocyanate (MDI), 260g of dimethyl carbonate, 40g of dimethylformamide, 40g of ethyl acetate, 0.5g of bismuth laurate, 5g of Trimethylolpropane (TMP) and 1g of phosphoric acid.
The preparation method of the low-temperature-resistant polyurethane composite adhesive comprises the following steps:
(1) Adding 20g of terephthalic acid, 142g of phthalic anhydride, 20g of isophthalic acid, 60g of hydroquinone diisopropyl ether, 90g of 2,2' - [1,4-phenylenebis (oxy-2,1-ethylenedioxy) ] diethanol, 62.5g of triethylene glycol and 50g of neopentyl glycol into a reaction kettle, heating to 140 ℃, gradually discharging water generated by the reaction after reaction water is discharged, heating to 5 ℃ every 10min, gradually heating to 225 ℃ and then preserving heat;
(2) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified, keeping the pressure at 0.5 standard atmosphere for 1h, then vacuumizing, and keeping the pressure at 500Pa for 2.2h; in this example, a sample was taken to determine that the acid value was 23.4mgKOH/g;
(3) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sampling test is qualified, then cooling to 55 ℃, and pressing into a glue reaction kettle; in this example, the acid value was measured by sampling and found to be 0.3mgK0H/g, and the hydroxyl value was measured to be 56.1mgK0H/g;
(4) Adding 40g of terephthalic acid, 18g of phthalic anhydride, 20g of isophthalic acid, 30g of succinic acid and 37.5g of triethylene glycol into a reaction kettle, heating to 140 ℃, gradually discharging water generated by the reaction after reaction water is discharged, heating to 5 ℃ every 20min, gradually heating to 225 ℃, and then preserving heat;
(5) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified, keeping the pressure at 0.5 standard atmosphere for 1h, then vacuumizing, and keeping the pressure at 500Pa for 2.2h; in this example, a sample was taken to determine that the acid value was 19.8mgKOH/g;
(6) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sampling test is qualified, then cooling to 55 ℃, and pressing into a glue reaction kettle; in this example, the acid value was measured by sampling and found to be 0.2mgK0H/g, and the hydroxyl value was measured to be 57.5mgK0H/g;
(7) Adding 30g of TDI, 80g of MDI, 130g of dimethyl carbonate, 40g of dimethylformamide, 40g of ethyl acetate, 0.5g of bismuth laurate and 5g of TMP into a glue reaction kettle, and reacting for 2.2h at 80 ℃;
(8) Adding 1g of phosphoric acid and 130g of dimethyl carbonate into a glue reaction kettle, sampling to measure the solid content and the viscosity, wherein the solid content is 65-66% when the sampling test is qualified, the viscosity is 150-160 Pa.s (25 ℃), and then discharging to obtain the low-temperature resistant polyurethane composite glue. The sample taken in this example showed a solids content of 65.5% and a viscosity of 156 pas (25 ℃).
Example 13
The low-temperature-resistant polyurethane composite adhesive is prepared from the following raw materials:
60g of terephthalic acid, 300g of phthalic anhydride, 40g of isophthalic acid, 90g of hydroquinone diisopropoxide ether 60g of 2,2' - [1,4-phenylenebis (oxy-2,1-ethanediyloxy) ] diethanol, 150g of neopentyl glycol, 30g of succinic acid, 30g of Toluene Diisocyanate (TDI), 80g of diphenylmethane diisocyanate (MDI), 260g of dimethyl carbonate, 40g of dimethylformamide, 40g of ethyl acetate, 0.5g of bismuth laurate, 5g of Trimethylolpropane (TMP) and 1g of phosphoric acid.
The preparation method of the low-temperature-resistant polyurethane composite adhesive comprises the following steps:
(1) Adding 20g of terephthalic acid, 240g of phthalic anhydride, 20g of isophthalic acid, 60g of hydroquinone diisopropanol ether, 2,2' - [1,4-phenylenebis (oxy-2,1-ethylenedioxy) ] diethanol and 112.5g of neopentyl glycol into a reaction kettle, heating to 140 ℃, gradually discharging water generated by the reaction after reaction water is discharged, heating to 5 ℃ every 10min, gradually heating to 225 ℃, and then preserving heat;
(2) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified, keeping the pressure at 0.5 standard atmosphere for 1h, then vacuumizing, and keeping the pressure at 500Pa for 2.2h; in this example, the acid value was measured by sampling and found to be 23.4mgKOH/g;
(3) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sampling test is qualified, then cooling to 55 ℃, and pressing into a glue reaction kettle; in this example, a sample was taken to determine that the acid value was 0.3mgK0H/g and the hydroxyl value was 53.4mgK0H/g;
(4) Adding 40g of terephthalic acid, 60g of phthalic anhydride, 20g of isophthalic acid, 30g of succinic acid and 37.5g of neopentyl glycol into a reaction kettle, heating to 140 ℃, gradually discharging water generated by the reaction after the reaction is performed, heating to 5 ℃ every 20min, gradually heating to 225 ℃, and then preserving heat;
(5) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified, keeping the pressure at 0.5 standard atmosphere for 1h, then vacuumizing, and keeping the pressure at 500Pa for 2.2h; in this example, the acid value was measured by sampling and was 21.6mgKOH/g;
(6) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sampling test is qualified, then cooling to 55 ℃, and pressing into a glue reaction kettle; in this example, the acid value was measured by sampling and found to be 0.2mgK0H/g, and the hydroxyl value was measured to be 56.1mgK0H/g;
(7) Adding 30g of TDI, 80g of MDI, 130g of dimethyl carbonate, 40g of dimethylformamide, 40g of ethyl acetate, 0.5g of bismuth laurate and 5g of TMP into a glue reaction kettle, and reacting for 2.2h at 80 ℃;
(8) Adding 1g of phosphoric acid and 130g of dimethyl carbonate into a glue reaction kettle, sampling to measure the solid content and the viscosity, wherein the solid content is 65-66% when the sample is qualified, the viscosity is 150-160 pas (25 ℃), and discharging to obtain the low-temperature-resistant polyurethane composite glue. The sample taken in this example showed a solids content of 65.2% and a viscosity of 154 pas (25 ℃).
Examples 14 to 18
Examples 14 to 18 are the same as example 13, except that the components of the B component are different, as shown in Table 2:
TABLE 2 contents of some components of examples 14 to 18
Figure BDA0003867529460000101
Example 19
Example 19 is the same as example 12 except that 0.005g of antioxidant 168 was also added to the glue pot for reaction in step (7).
Example 20
The low-temperature-resistant polyurethane composite adhesive is prepared from the following raw materials:
210g of phthalic anhydride, 50g of isophthalic acid, 80g of hydroquinone diisopropanol ether, 2' - [1,4-phenylene bis (oxy-2,1-ethanediyloxy) ] diethanol, 100g of triethylene glycol, 50g of butanediol, 10g of sebacic acid, 80g of Toluene Diisocyanate (TDI), 30g of isophorone diisocyanate (IPDI), 260g of dimethyl carbonate, 40g of dimethylformamide, 40g of ethyl acetate, 0.5g of bismuth laurate, 5g of glycerol and 1g of phosphoric acid.
The preparation method of the low-temperature-resistant polyurethane composite adhesive comprises the following steps:
(1) 200g of phthalic anhydride, 21g of isophthalic acid, 80g of hydroquinone diisopropyl ether, 70g of 2,2' - [1,4-phenylene bis (oxy-2,1-ethanediyloxy) ] diethanol, 62.5g of triethylene glycol and 50g of butanediol are added into a reaction kettle, the temperature is raised to 140 ℃, after reaction water is discharged, water generated by the reaction is gradually discharged, the temperature is raised to 5 ℃ every 10min, the temperature is gradually raised to 225 ℃, and then the temperature is maintained;
(2) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified, keeping the pressure at 0.5 standard atmosphere for 1h, then vacuumizing, and keeping the pressure at 500Pa for 2.2h; in this example, a sample was taken to determine that the acid value was 11.6mgKOH/g;
(3) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sampling test is qualified, then cooling to 55 ℃, and pressing into a glue reaction kettle; in this example, the acid value was measured by sampling and was 0.2mgK0H/g, and the hydroxyl value was measured to be 56.4mgK0H/g;
(4) Adding 10g of phthalic anhydride, 29g of isophthalic acid, 10g of sebacic acid and 37.5g of triethylene glycol into a reaction kettle, heating to 140 ℃, gradually discharging water generated by the reaction after the reaction is performed, heating to 5 ℃ every 20min, gradually heating to 225 ℃, and then preserving heat;
(5) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified, keeping the pressure at 0.5 standard atmosphere for 1h, then vacuumizing, and keeping the pressure at 500Pa for 2.2h; in this example, the acid value was measured by sampling and was 12.5mgKOH/g;
(6) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sampling test is qualified, then cooling to 55 ℃, and pressing into a glue reaction kettle; in this example, the acid value was measured to be 0.4mgK0H/g and the hydroxyl value was measured to be 54.1mgK0H/g;
(7) Adding 80g of TDI, 30g of IPDI, 130g of dimethyl carbonate, 40g of dimethylformamide, 40g of ethyl acetate, 0.5g of bismuth laurate and 5g of glycerol into a glue reaction kettle, and reacting for 2.2h at 80 ℃;
(8) Adding 1g of phosphoric acid and 130g of dimethyl carbonate into a glue reaction kettle, sampling to measure the solid content and the viscosity, wherein the solid content is 65-66% when the sampling test is qualified, the viscosity is 150-160 Pa.s (25 ℃), and then discharging to obtain the low-temperature resistant polyurethane composite glue. The sample taken in this example showed a solids content of 65.2% and a viscosity of 155 pas (25 ℃).
Examples 21 to 24
Examples 21 to 24 are the same as example 20 except that the composition and content of the aliphatic polybasic acid in step (4) are different, as shown in Table 3:
TABLE 3 composition and content of aliphatic polybasic acid in examples 14 to 18, step (4)
Figure BDA0003867529460000111
Figure BDA0003867529460000121
Example 25
Example 25 is the same as example 21 except that 0.3g of bismuth laurate was used in step (7).
Example 26
Example 26 is the same as example 21 except that 0.6g of bismuth laurate was used in step (7).
Examples 27 to 30
Examples 27 to 30 are the same as example 21 except that the composition and content of the crosslinking agent in step (7) are different, as shown in Table 4:
TABLE 4 compositions and amounts of aliphatic polybasic acids in examples 27-30, step (4)
Figure BDA0003867529460000122
Example 31
Example 31 is the same as example 21 except that 0.005g of antioxidant 168 was also added to the glue pot for reaction in step (7).
Example 32
The low-temperature-resistant polyurethane composite adhesive is prepared from the following raw materials:
200g of phthalic anhydride, 60g of isophthalic acid, 60g of hydroquinone diisopropyl ether, 2' - [1,4-phenylenebis (oxy-2,1-ethanediyloxy) ] diethanol 90g, 100g of triethylene glycol, 50g of diethylene glycol, 30g of adipic acid, 90g of Toluene Diisocyanate (TDI), 260g of dimethyl carbonate, 40g of dimethylformamide, 40g of ethyl acetate, 0.5g of bismuth laurate, 5g of Trimethylolpropane (TMP) and 1g of phosphoric acid.
The preparation method of the low-temperature-resistant polyurethane composite adhesive comprises the following steps:
(1) 200g of phthalic anhydride, 60g of hydroquinone diisopropyl ether, 2,2' - [1,4-phenylene bis (oxy-2,1-ethanediyloxy) ] diethanol 90g, 62.5g of triethylene glycol and 50g of diethylene glycol are added into a reaction kettle, the temperature is raised to 140 ℃, after reaction water is discharged, the water generated by the reaction is gradually discharged, the temperature is raised to 5 ℃ every 10min, the temperature is gradually raised to 225 ℃, and then the temperature is maintained;
(2) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified, keeping the pressure at 0.5 standard atmosphere for 1h, then vacuumizing, and keeping the pressure at 500Pa for 2.2h; in this example, a sample was taken to determine that the acid value was 9.5mgKOH/g;
(3) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sampling test is qualified, then cooling to 55 ℃, and pressing into a glue reaction kettle; in this example, the acid value was measured by sampling and was 0.3mgK0H/g, and the hydroxyl value was measured to be 57.5mgK0H/g;
(4) Adding 60g of isophthalic acid, 30g of adipic acid and 37.5g of triethylene glycol into a reaction kettle, heating to 140 ℃, gradually discharging water generated by the reaction after reaction water is discharged, heating to 5 ℃ every 20min, gradually heating to 225 ℃, and then preserving heat;
(5) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified, keeping the pressure at 0.5 standard atmosphere for 1h, then vacuumizing, and keeping the pressure at 500Pa for 2.2h; in this example, a sample was taken to determine that the acid value was 12.5mgKOH/g;
(6) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sampling test is qualified, then cooling to 55 ℃, and pressing into a glue reaction kettle; in this example, the acid value was measured by sampling and found to be 0.2mgK0H/g, and the hydroxyl value was measured to be 57.1mgK0H/g;
(7) Adding 80g of TDI, 30g of IPDI, 130g of dimethyl carbonate, 40g of dimethylformamide, 40g of ethyl acetate, 0.5g of bismuth laurate and 5g of TMP into a glue reaction kettle, and reacting for 2.2h at 80 ℃;
(8) Adding 1g of phosphoric acid and 130g of dimethyl carbonate into a glue reaction kettle, sampling to measure the solid content and the viscosity, wherein the solid content is 65-66% when the sample is qualified, the viscosity is 150-160 pas (25 ℃), and discharging to obtain the low-temperature-resistant polyurethane composite glue. The sample taken in this example showed a solids content of 65.5% and a viscosity of 152 pas (25 ℃).
Examples 33 to 35
Examples 33 to 35 are identical to example 32, with the difference that in step (7) a different content of Hexamethylene Diisocyanate (HDI) is also added, see in particular Table 5:
TABLE 5 content of hexamethylene diisocyanate added in step (7) in examples 33 to 35
Examples Hexamethylene diisocyanate/g
Example 32 0
Example 33 20
Example 34 40
Example 35 60
Example 36
Example 36 is the same as example 33 except that 0.05g of monthly phosphoric acid is used in step (8).
Example 37
Example 37 is the same as example 33 except that 0.2g of phosphoric acid is used in step (8).
Example 38
Example 38 is the same as example 33 except that 0.005g of antioxidant 168 was also added to the glue pot for reaction in step (7).
Example 39
The low-temperature-resistant polyurethane composite adhesive is prepared from the following raw materials:
170g of phthalic anhydride, 90g of isophthalic acid, 100g of hydroquinone diisopropanol ether, 50g of 2,2' - [1,4-phenylenebis (oxy-2,1-ethanediyloxy) ] diethanol, 140g of triethylene glycol, 10g of ethylene glycol, 30g of adipic acid, 110g of Toluene Diisocyanate (TDI), 120g of dimethyl carbonate, 40g of dimethylformamide, 40g of ethyl acetate, 0.5g of bismuth laurate, 5g of glycerol and 1g of phosphoric acid.
The preparation method of the low-temperature-resistant polyurethane composite adhesive comprises the following steps:
(1) Adding 170g of phthalic anhydride, 30g of isophthalic acid, 100g of hydroquinone diisopropyl ether, 50g of 2,2' - [1,4-phenylene bis (oxy-2,1-ethylene glycol oxy) ] diethanol and 112.5g of triethylene glycol into a reaction kettle, heating to 140 ℃, gradually discharging water generated by the reaction after reaction water is discharged, heating to 5 ℃ every 10min, gradually heating to 225 ℃, and then keeping the temperature;
(2) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified, keeping the pressure at 0.5 standard atmosphere for 1h, then vacuumizing, and keeping the pressure at 500Pa for 2.2h; in this example, the acid value was measured by sampling and was 13.6mgKOH/g;
(3) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sampling test is qualified, then cooling to 55 ℃, and pressing into a glue reaction kettle; in this example, the acid value was measured by sampling and found to be 0.2mgK0H/g, and the hydroxyl value was measured to be 53.1mgK0H/g;
(4) Adding 60g of isophthalic acid, 27.5g of triethylene glycol, 10g of ethylene glycol and 30g of adipic acid into a reaction kettle, heating to 140 ℃, gradually discharging water generated by the reaction after reaction water is discharged, heating to 5 ℃ every 20min, gradually heating to 225 ℃, and then preserving heat;
(5) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified, keeping the pressure at 0.5 standard atmosphere for 1h, then vacuumizing, and keeping the pressure at 500Pa for 2.2h; in this example, the acid value was measured by sampling and was 12.5mgKOH/g;
(6) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sampling test is qualified, then cooling to 55 ℃, and pressing into a glue reaction kettle; in this example, the acid value was measured by sampling and found to be 0.3mgK0H/g, and the hydroxyl value was measured to be 54.1mgK0H/g;
(7) Adding TDI110g, dimethyl carbonate 20g, dimethylformamide 40g, ethyl acetate 40g, bismuth laurate 0.5g and TMP5g into a glue reaction kettle, and reacting at 80 ℃ for 2.2h;
(8) Adding 1g of phosphoric acid and 100g of dimethyl carbonate into a glue reaction kettle, sampling to measure the solid content and the viscosity, wherein the solid content is 65-66% when the sampling test is qualified, the viscosity is 150-160 Pa.s (25 ℃), and then discharging to obtain the low-temperature resistant polyurethane composite glue. The sample taken in this example showed a solids content of 65.9% and a viscosity of 158 pas (25 ℃).
Examples 40 to 42
Examples 40 to 42 are the same as example 39 except that the amount of dimethyl carbonate added in step (7) was different, as shown in Table 6:
TABLE 6 addition of dimethyl carbonate in step (7) of examples 40 to 42
Examples Dimethyl carbonate/g
Example 40 20
Example 41 26
Example 42 32
Example 43
The low-temperature-resistant polyurethane composite adhesive is prepared from the following raw materials:
170g of phthalic anhydride, 90g of isophthalic acid, 100g of hydroquinone diisopropanol ether, 50g of 2,2' - [1,4-phenylenebis (oxy-2,1-ethanediyloxy) ] diethanol, 140g of triethylene glycol, 10g of ethylene glycol, 30g of adipic acid, 110g of Toluene Diisocyanate (TDI), 260g of dimethyl carbonate, 80g of dimethylformamide, 0.5g of bismuth laurate, 5g of glycerol and 1g of phosphoric acid.
The preparation method of the low-temperature-resistant polyurethane composite adhesive comprises the following steps:
(1) Adding 170g of phthalic anhydride, 30g of isophthalic acid, 100g of hydroquinone diisopropyl ether, 50g of 2,2' - [1,4-phenylene bis (oxy-2,1-ethanediyloxy) ] diethanol and 112.5g of triethylene glycol into a reaction kettle, heating to 140 ℃, gradually discharging water generated by the reaction after reaction water is discharged, heating to 5 ℃ every 10min, gradually heating to 225 ℃, and then preserving heat;
(2) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified, then keeping the pressure at 0.5 standard atmosphere for 1 hour, vacuumizing, and keeping the pressure at 500Pa for 2.2 hours; in this example, the acid value was measured by sampling and found to be 18.6mgKOH/g;
(3) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sample is qualified in the sampling test, then cooling to 55 ℃, and pressing into a glue reaction kettle; in this example, the acid value was measured by sampling and found to be 0.2mgK0H/g, and the hydroxyl value was measured to be 54.7mgK0H/g;
(4) Adding 60g of isophthalic acid, 27.5g of triethylene glycol, 10g of ethylene glycol and 30g of adipic acid into a reaction kettle, heating to 140 ℃, gradually discharging water generated by the reaction after reaction water is discharged, heating to 5 ℃ every 20min, gradually heating to 225 ℃, and then preserving heat;
(5) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified, keeping the pressure at 0.5 standard atmosphere for 1h, then vacuumizing, and keeping the pressure at 500Pa for 2.2h; in this example, the acid value was measured by sampling and was 13.6mgKOH/g;
(6) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sampling test is qualified, then cooling to 55 ℃, and pressing into a glue reaction kettle; in this example, the acid value was measured by sampling and found to be 0.3mgK0H/g, and the hydroxyl value was measured to be 54.1mgK0H/g;
(7) Adding TDI110g, dimethyl carbonate 90g, dimethyl formamide 80g, bismuth laurate 0.5g and TMP5g into a glue reaction kettle, and reacting at 80 ℃ for 2.2h;
(8) Adding 1g of phosphoric acid and 170g of dimethyl carbonate into a glue reaction kettle, sampling to measure the solid content and the viscosity, wherein the solid content is 65-66% when the sampling test is qualified, the viscosity is 150-160 Pa.s (25 ℃), and then discharging to obtain the low-temperature resistant polyurethane composite glue. The sampling test in this example gave a solids content of 65.3% and a viscosity of 156 pas (25 ℃ C.).
Example 44
The low-temperature-resistant polyurethane composite adhesive is prepared from the following raw materials:
170g of phthalic anhydride, 90g of isophthalic acid, 100g of hydroquinone diisopropanol ether, 50g of 2,2' - [1,4-phenylenebis (oxy-2,1-ethanediyloxy) ] diethanol, 140g of triethylene glycol, 10g of ethylene glycol, 30g of adipic acid, 110g of Toluene Diisocyanate (TDI), 340g of dimethyl carbonate, 0.5g of bismuth laurate, 5g of glycerol and 1g of phosphoric acid.
The preparation method of the low-temperature-resistant polyurethane composite adhesive comprises the following steps:
(1) Adding 170g of phthalic anhydride, 30g of isophthalic acid, 100g of hydroquinone diisopropyl ether, 50g of 2,2' - [1,4-phenylene bis (oxy-2,1-ethanediyloxy) ] diethanol and 112.5g of triethylene glycol into a reaction kettle, heating to 140 ℃, gradually discharging water generated by the reaction after reaction water is discharged, heating to 5 ℃ every 10min, gradually heating to 225 ℃, and then preserving heat;
(2) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified, keeping the pressure at 0.5 standard atmosphere for 1h, then vacuumizing, and keeping the pressure at 500Pa for 2.2h; in this example, the acid value was measured by sampling and found to be 19.2mgKOH/g;
(3) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sampling test is qualified, then cooling to 55 ℃, and pressing into a glue reaction kettle; in this example, the acid value was measured by sampling and was 0.3mgK0H/g, and the hydroxyl value was measured to be 57.5mgK0H/g;
(4) Adding 60g of isophthalic acid, 27.5g of triethylene glycol, 10g of ethylene glycol and 30g of adipic acid into a reaction kettle, heating to 140 ℃, gradually discharging water generated by the reaction after reaction water is discharged, heating to 5 ℃ every 20min, gradually heating to 225 ℃, and then preserving heat;
(5) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified, keeping the pressure at 0.5 standard atmosphere for 1h, then vacuumizing, and keeping the pressure at 500Pa for 2.2h; in this example, the acid value was measured by sampling and was 12.4mgKOH/g;
(6) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sampling test is qualified, then cooling to 55 ℃, and pressing into a glue reaction kettle; in this example, the acid value was measured to be 0.4mgK0H/g and the hydroxyl value was measured to be 54.9mgK0H/g;
(7) Adding 110g of TDI, 170g of dimethyl carbonate, 0.5g of bismuth laurate and 5g of TMP into a glue reaction kettle, and reacting for 2.2h at 80 ℃;
(8) Adding 1g of phosphoric acid and 170g of dimethyl carbonate into a glue reaction kettle, sampling to measure the solid content and the viscosity, wherein the solid content is 65-66% when the sampling test is qualified, the viscosity is 150-160 Pa.s (25 ℃), and then discharging to obtain the low-temperature resistant polyurethane composite glue. The sampling test in this example gave a solids content of 65.7% and a viscosity of 156 pas (25 ℃ C.).
Example 45
Example 45 is the same as example 41 except that 0.005g of antioxidant 168 was also added to the glue pot for reaction in step (7).
The differences in the values of the sampling tests in the partial steps during the preparation of examples 1 to 45 are shown in Table 7:
TABLE 7 values of partial step sampling tests in the preparation of examples 1 to 45
Figure BDA0003867529460000171
Figure BDA0003867529460000181
Figure BDA0003867529460000191
Figure BDA0003867529460000201
Figure BDA0003867529460000211
Figure BDA0003867529460000221
Figure BDA0003867529460000231
Comparative example
Comparative example 1
The low-temperature-resistant polyurethane composite adhesive is prepared from the following raw materials:
50g of terephthalic acid, 210g of phthalic anhydride, 200g of triethylene glycol, 100g of diethylene glycol, 30g of adipic acid, 30g of Toluene Diisocyanate (TDI), 80g of diphenylmethane diisocyanate (MDI), 260g of dimethyl carbonate, 40g of dimethylformamide, 40g of ethyl acetate, 0.5g of bismuth laurate, 5g of Trimethylolpropane (TMP) and 1g of phosphoric acid.
The preparation method of the low-temperature-resistant polyurethane composite adhesive comprises the following steps:
2. adding 50g of terephthalic acid, 150g of phthalic anhydride, 162.5g of triethylene glycol and 100g of diethylene glycol into a reaction kettle, heating to 140 ℃, gradually discharging water generated by the reaction after the reaction is performed, heating to 5 ℃ every 10min, gradually heating to 225 ℃, and then preserving heat;
(2) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified, then keeping the pressure at 0.5 standard atmosphere for 1 hour, vacuumizing, and keeping the pressure at 500Pa for 2.2 hours; in this example, the acid value was measured by sampling and found to be 22.3mgKOH/g;
(3) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sample is qualified in the sampling test, then cooling to 55 ℃, and pressing into a glue reaction kettle; in this example, the acid value was measured by sampling and was 0.3mgK0H/g, and the hydroxyl value was measured to be 54.3mgK0H/g;
(4) Adding 60g of phthalic anhydride, 30g of adipic acid and 37.5g of triethylene glycol into a reaction kettle, heating to 140 ℃, gradually discharging water generated by the reaction after reaction water is discharged, heating to 5 ℃ every 20min, gradually heating to 225 ℃, and then preserving heat;
(5) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified, keeping the pressure at 0.5 standard atmosphere for 1h, then vacuumizing, and keeping the pressure at 500Pa for 2.2h; in this example, the acid value was measured by sampling and was 21.4mgKOH/g;
(6) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sampling test is qualified, then cooling to 55 ℃, and pressing into a glue reaction kettle; in this example, the acid value was measured to be 0.4mgK0H/g and the hydroxyl value was measured to be 56.8mgK0H/g;
(7) Adding 30g of TDI, 80g of MDI, 130g of dimethyl carbonate, 40g of dimethylformamide, 40g of ethyl acetate, 0.5g of bismuth laurate and 5g of TMP into a glue reaction kettle, and reacting for 2.2h at 80 ℃;
(8) Adding 1g of phosphoric acid and 130g of dimethyl carbonate into a glue reaction kettle, sampling to measure the solid content and the viscosity, wherein the solid content is 65-66% when the sampling test is qualified, the viscosity is 150-160 Pa.s (25 ℃), and then discharging to obtain the low-temperature resistant polyurethane composite glue. The sample taken in this example showed a solids content of 65.7% and a viscosity of 152 pas (25 ℃).
Detection method
The performance test of the low-temperature resistant polyurethane composite adhesive adopts the following scheme:
1. and (3) viscosity testing: the low temperature resistant polyurethane composite glues obtained in examples 1 to 45 and comparative example 1 were tested for viscosity at 0 deg.C, -5 deg.C, -10 deg.C using a Brookfield viscometer with a 27# spindle and 20rpm/min, respectively.
2. Embrittlement temperature test: the brittle temperature of the low temperature resistant polyurethane compound glue prepared in the examples 1-45 and the comparative example 1 is tested by referring to GB/T5470-2008 determination of the catalytic temperature by the plastic impact method.
The test results are shown in table 8:
TABLE 8 results of performance test of low temperature resistant polyurethane composite adhesives obtained in examples 1 to 45 and comparative example 1
Figure BDA0003867529460000241
Figure BDA0003867529460000251
Figure BDA0003867529460000261
Comparing examples 1 to 9 with comparative example 1, the low temperature resistant polyurethane compound glues prepared in examples 1 to 9 all have a viscosity of less than 725 at-10 ℃ and have a certain fluidity, while the low temperature resistant polyurethane compound glue prepared in comparative example 1 is frozen at-10 ℃ and the viscosity cannot be measured, so that the fluidity of the low temperature resistant polyurethane compound glues prepared in examples 1 to 9 at-10 ℃ is better than that of comparative example 1, and it is shown that the component A helps to improve the low temperature resistance of the low temperature resistant polyurethane compound glue.
Comparing examples 1 to 9 with comparative example 1, the brittle temperature of the low temperature resistant polyurethane compound glue prepared by examples 1 to 9 is lower than-56 ℃, while the brittle temperature of the low temperature resistant polyurethane compound glue prepared by comparative example 1 is-62 ℃, so that the low temperature resistant polyurethane compound glue prepared by examples 1 to 9 has better flexibility at low temperature than comparative example 1, and the A component is helpful for improving the flexibility of the low temperature resistant polyurethane compound glue at low temperature.
In comparison with examples 1 to 3 or examples 4 to 6, the embrittlement temperature of the low temperature resistant polyurethane composite adhesive is significantly reduced with the increase of the content of the component a in the low temperature resistant polyurethane composite adhesive, which shows that increasing the content of the component a contributes to the improvement of the flexibility of the low temperature resistant polyurethane composite adhesive at low temperature.
Compared with the comparative example 2, the example 5 and the examples 7 to 9, the embrittlement of the low-temperature resistant polyurethane composite adhesive can be further reduced by compounding the hydroquinone diisopropyl ether and the 2,2' - [1,4-phenylene bis (oxy-2,1-ethylenedioxy) ] diethanol, which shows that the effect of compounding the hydroquinone diisopropyl ether and the 2,2' - [1,4-phenylene bis (oxy-2,1-ethylenedioxy) ] diethanol is better than that of compounding the hydroquinone diisopropyl ether and the 2,2' - [1,4-phenylene bis (oxy-2,1-ethylenedioxy) ] diethanol.
In comparative examples 11 to 18, the embrittlement of the low temperature resistant polyurethane composite adhesive can be further reduced by the component B obtained by compounding a plurality of polyols, which shows that the effect of the component B obtained by compounding the polyols is better than that of the single component.
In comparison with examples 20 to 22, the embrittlement temperature of the low temperature resistant polyurethane composite adhesive is significantly reduced with the increase of the content of the aliphatic polybasic acid in the low temperature resistant polyurethane composite adhesive, which indicates that the increase of the content of the aliphatic polybasic acid is helpful for improving the flexibility of the low temperature resistant polyurethane composite adhesive at a low temperature.
Compared with the embodiment 21 and the embodiment 23, the embrittlement of the low-temperature resistant polyurethane composite adhesive can be further reduced by compounding a plurality of aliphatic polybasic acids, which shows that the compounding effect of the plurality of aliphatic polybasic acids is better than that of a single component.
In comparative examples 39 to 42, the viscosity of the low temperature resistant polyurethane composite adhesive at low temperature is significantly reduced with the increase of the solvent content in the low temperature resistant polyurethane composite adhesive, which indicates that increasing the solvent content is helpful for improving the flexibility of the low temperature resistant polyurethane composite adhesive at low temperature.
The specific embodiments are only for explaining the present application and are not limiting to the present application, and those skilled in the art can make modifications to the embodiments without inventive contribution as required after reading the present specification, but all the embodiments are protected by patent law within the scope of the claims of the present application.

Claims (10)

1. A low temperature resistant polyurethane composite adhesive is characterized in that: the paint comprises the following components in parts by weight:
20-40 parts of aromatic polybasic acid;
20-40 parts of polyol;
5-8 parts of aliphatic polybasic acid;
9-15 parts of polyisocyanate;
20-40 parts of a solvent;
0.03-0.06 part of catalyst;
0.1-1 part of cross-linking agent;
0.05 to 0.2 portion of terminator;
the polyol comprises a component A, and the component A is selected from one or more of hydroquinone diisopropyl ether and 2,2' - [1,4-phenylene bis (oxy-2,1-ethanediyloxy) ] diethanol.
2. The low temperature resistant polyurethane laminating adhesive of claim 1, wherein: the solvent is selected from one or more of dimethyl carbonate, dimethyl formamide and ethyl acetate.
3. The low temperature resistant polyurethane laminating adhesive of claim 1, wherein: the aliphatic polybasic acid is selected from one or more of adipic acid, sebacic acid and succinic acid.
4. The low temperature resistant polyurethane laminating adhesive of claim 1, wherein: the polyalcohol also comprises a component B, wherein the component B is one or more selected from diethylene glycol, ethylene glycol, triethylene glycol, neopentyl glycol, hexanediol and butanediol.
5. The low temperature resistant polyurethane laminating adhesive of claim 1, wherein: the polyisocyanate comprises one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) and Hexamethylene Diisocyanate (HDI).
6. The low temperature resistant polyurethane laminating adhesive of claim 1, wherein: the aromatic polybasic acid is selected from one or more of terephthalic acid, phthalic anhydride and isophthalic acid.
7. The low temperature resistant polyurethane laminating adhesive of claim 1, wherein: the catalyst is bismuth neodecanoate.
8. The low temperature resistant polyurethane laminating adhesive of claim 1, wherein: the cross-linking agent is selected from one or more of Trimethylolpropane (TMP) and glycerol.
9. The preparation method of the low temperature resistant polyurethane laminating adhesive of any one of claims 1 to 8, characterized by comprising the following steps:
(1) Adding 70-85 wt% of aromatic polybasic acid, 75 wt% of component A and component B into a reaction kettle, heating to 140-150 ℃, discharging water generated by the reaction step by step after reaction water is discharged, heating to 5 ℃ every 10min, heating to 225 ℃ step by step, and keeping the temperature;
(2) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified; after the requirement is met, keeping the pressure for 1 to 2 hours under 0.4 to 0.6 standard atmospheric pressure, and then keeping the pressure for 2 to 3 hours under 300 to 1000 pa;
(3) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sampling test is qualified; cooling to 50-60 ℃ after the requirement is met, and pressing into a glue reaction kettle;
(4) Adding aliphatic polybasic acid, residual aromatic polybasic acid and residual component B into a reaction kettle, heating to 140-150 ℃, gradually discharging water generated by the reaction after reaction water is discharged, heating to 5 ℃ every 20min, gradually heating to 225 ℃, and then preserving heat;
(5) Sampling to test the acid value, wherein the acid value is 0-30 mgKOH/g when the sampling test is qualified; after the requirement is met, keeping the pressure for 1 to 2 hours under 0.4 to 0.6 standard atmospheric pressure, and then keeping the pressure for 2 to 3 hours under 300 to 1000 pa;
(6) Sampling to test the acid value and the hydroxyl value, wherein the acid value is 0-0.5mgK0H/g and the hydroxyl value is 53-59 mgK0H/g when the sampling test is qualified, cooling to 50-60 ℃ after the requirement is met, and pressing into a glue reaction kettle;
(7) Adding partial solvent, cross-linking agent and catalyst into the glue reaction kettle at 80-85 ℃ to react for 2-3 h;
(8) Adding a terminating agent and the residual solvent, sampling to measure the solid content and the viscosity, and discharging after the requirements are met to obtain the low-temperature-resistant polyurethane composite adhesive.
10. The preparation method of the low temperature resistant polyurethane laminating adhesive according to claim 9, characterized in that: when the sample in the step (8) is qualified in the test, the solid content is 65-66%, and the viscosity is 150-160 Pa.s (25 ℃).
CN202211182879.7A 2022-09-27 2022-09-27 Low-temperature-resistant polyurethane composite adhesive and preparation method thereof Pending CN115537171A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1244851A (en) * 1967-08-22 1971-09-02 Elastomer Ag Method of producing heat-resisting mouldable polyurethane elastomers
FR2235146A1 (en) * 1973-06-26 1975-01-24 Dai Ichi Kogyo Seiyaku Co Ltd
ATA326378A (en) * 1976-08-05 1979-09-15 Polyair Maschinenbau Gmbh PROCESS FOR THE PRODUCTION OF NEW ANTHRANIL ACID ESTERS
US4283548A (en) * 1979-04-10 1981-08-11 Lim-Holding S.A Diisatoic acid or triisatoic acid derivatives
US6359101B1 (en) * 1999-12-15 2002-03-19 Synuthane International, Inc. Preparing polyether polyols with DMC catalysts
CN106833487A (en) * 2017-01-19 2017-06-13 湖州倍格曼新材料股份有限公司 A kind of high initial bonding strength polyurethane composite gel and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1244851A (en) * 1967-08-22 1971-09-02 Elastomer Ag Method of producing heat-resisting mouldable polyurethane elastomers
FR2235146A1 (en) * 1973-06-26 1975-01-24 Dai Ichi Kogyo Seiyaku Co Ltd
ATA326378A (en) * 1976-08-05 1979-09-15 Polyair Maschinenbau Gmbh PROCESS FOR THE PRODUCTION OF NEW ANTHRANIL ACID ESTERS
US4283548A (en) * 1979-04-10 1981-08-11 Lim-Holding S.A Diisatoic acid or triisatoic acid derivatives
US6359101B1 (en) * 1999-12-15 2002-03-19 Synuthane International, Inc. Preparing polyether polyols with DMC catalysts
CN106833487A (en) * 2017-01-19 2017-06-13 湖州倍格曼新材料股份有限公司 A kind of high initial bonding strength polyurethane composite gel and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHUN-CHIEH HUANG等: ""Synthesis and evaluation of alkoxylated-ether diols of hydroquinone with different chain-lengths as extenders in segmented polyurethanes"", 《J. POLYM. RES.》, vol. 22, pages 1 - 11, XP035542106, DOI: 10.1007/s10965-015-0812-5 *
张晓华等: ""软段对IPDI基透明聚氨酯弹性体微相结构与性能的影响"", 《中国塑料》, vol. 19, no. 8, pages 27 *

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Application publication date: 20221230