CN112778958A - Polyurethane adhesive and colloid prepared from same - Google Patents
Polyurethane adhesive and colloid prepared from same Download PDFInfo
- Publication number
- CN112778958A CN112778958A CN202011625727.0A CN202011625727A CN112778958A CN 112778958 A CN112778958 A CN 112778958A CN 202011625727 A CN202011625727 A CN 202011625727A CN 112778958 A CN112778958 A CN 112778958A
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- China
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- polyurethane adhesive
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- polyol
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Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 57
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 57
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 35
- 239000004814 polyurethane Substances 0.000 title claims abstract description 35
- 239000000084 colloidal system Substances 0.000 title claims abstract description 24
- 239000004970 Chain extender Substances 0.000 claims abstract description 40
- 229920005862 polyol Polymers 0.000 claims abstract description 34
- 150000003077 polyols Chemical class 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000945 filler Substances 0.000 claims abstract description 25
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 22
- 229920000570 polyether Polymers 0.000 claims abstract description 22
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 21
- 239000012765 fibrous filler Substances 0.000 claims abstract description 13
- 239000002250 absorbent Substances 0.000 claims abstract description 11
- 230000002745 absorbent Effects 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 239000012948 isocyanate Substances 0.000 claims abstract description 6
- 239000006254 rheological additive Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 17
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- XPFCZYUVICHKDS-UHFFFAOYSA-N 3-methylbutane-1,3-diol Chemical compound CC(C)(O)CCO XPFCZYUVICHKDS-UHFFFAOYSA-N 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- 238000006757 chemical reactions by type Methods 0.000 claims description 5
- 150000002513 isocyanates Chemical group 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- SIMYRXPCIUXDGR-UHFFFAOYSA-N 2-butylpropane-1,3-diol Chemical compound CCCCC(CO)CO SIMYRXPCIUXDGR-UHFFFAOYSA-N 0.000 claims description 3
- YVHAOWGRHCPODY-UHFFFAOYSA-N 3,3-dimethylbutane-1,2-diol Chemical compound CC(C)(C)C(O)CO YVHAOWGRHCPODY-UHFFFAOYSA-N 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims description 3
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 claims description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 235000011067 sorbitan monolaureate Nutrition 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 230000035939 shock Effects 0.000 abstract description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011268 mixed slurry Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 150000001718 carbodiimides Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007541 indentation hardness test Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- 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
- C09J175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a polyurethane adhesive and a colloid prepared from the same, wherein the polyurethane adhesive comprises a component A and a component B; the component B is isocyanate prepolymer; the component A comprises the following components in parts by weight: 5-65 parts of polyol, 0-1 part of chain extender, 1-3 parts of cross-linking agent, 15-40 parts of filler, 1-3 parts of rheological additive, 5-15 parts of water absorbent and 0.1-0.3 part of catalyst; wherein the polyol is at least one of polyether polyol and polyester polyol; the filler is fibrous filler. The polyurethane adhesive has low colloid hardness and high bonding strength, and can meet the requirements of shock absorption and bearing.
Description
Technical Field
The invention relates to the technical field of adhesive materials, in particular to a polyurethane adhesive and a colloid prepared from the polyurethane adhesive.
Background
With the development of economic society, the technology of adhesive bonding and fixing is widely applied to the life of people due to the characteristics of light weight, simplicity and good sealing performance. However, compared with the traditional fixing mode (riveting, welding and the like), the bonding and fixing mode has lower strength and is not suitable for fixing structural members needing bearing, and the development of the high-strength adhesive capable of bearing is a constant topic in the bonding field. The adhesive strength of the adhesive and the hardness of the gel are generally in a positive correlation, which is very disadvantageous for application scenarios requiring both damping and load-bearing, for example, the fastening of vehicle seats, the fastening of battery cells. Therefore, the development of low hardness, high bond strength adhesives is of great importance for the broad range of bonding applications.
Disclosure of Invention
In view of the above, there is a need for a polyurethane adhesive and a colloid prepared therefrom. The polyurethane adhesive has low colloid hardness and high bonding strength, and can meet the requirements of shock absorption and bearing.
A polyurethane adhesive comprises a component A and a component B; the component B is isocyanate prepolymer;
the component A comprises the following components in parts by weight:
wherein the polyol is at least one of polyether polyol and polyester polyol;
the filler is fibrous filler.
In one embodiment, the polyol is a combination of a polyester polyol and a polyether polyol.
In one embodiment, the filler is at least one of glass fiber and calcium sulfate whisker.
In one embodiment, in the component a, 0.1 to 0.8 part of a chain extender is used, and the chain extender has a structure shown in formula (I):
R1-R10each independently is H or C1-4An alkyl group; and R is1-R10At least one of them is C1-4An alkyl group;
a. b and c are each independently 0, 1 or 2.
In one embodiment, the chain extender is an asymmetric chain extender.
In one embodiment, R1And R2In which one substituent is present with R9Is different from R10Are also different, and/or;
R3and R4In which one substituent is present with R7Is different from R8And are also different.
In one embodiment, the chain extender is at least one of 3, 3-dimethyl-1, 2-butanediol, 2-n-butyl-1, 3-propanediol, 3-methyl-1, 3-butanediol, and 2-methyl-2, 4-pentanediol.
In one embodiment, the catalyst is a water reaction inhibition type catalyst, and preferably the catalyst is one or more of Amicure KT-22, CuCat-HAA and CuCat-HAB; and/or
The water absorbent is at least one of calcium oxide and molecular sieve.
In one embodiment, the polyether polyol is at least one of A-600 produced by eastern Lanzhong, Sovermol 760, 805, 810, 815 produced by German Basff and bisphenol A-polyoxyethylene ether produced by Tianmen Changchang chemical industry; and/or
The polyester polyol is at least one of Span 20 produced by Shanghai Minkou chemical industry and PCL-2053 and 2055 produced by polymer kernel chemical industry; and/or
The cross-linking agent is at least one of glycerol, triethanolamine and G-12, G-18 and G-25 in petrochemical production of Jiangsu Haian; and/or
The rheological additive is at least one of R-974 and R-812 produced by Woodbis sp and H-20 produced by Wake chemical Co.
In one embodiment, the reaction raw materials of the component B comprise:
1000300 parts of polypropylene glycol
250-300 parts of carbodiimide-modified 44 diphenylmethane diisocyanate
0.01-0.05 part of catalyst.
The adhesive is prepared by mixing and curing the component A and the component B in the polyurethane adhesive.
In one embodiment, in the mixing of the A component and the B component, the mixing ratio of the A component and the B component is calculated by the molar ratio of OH in the A component to NCO in the B component being 1 (1.04-1.08).
Has the advantages that:
in the process of research, the technicians of the invention find that the traditional adhesive is generally prepared from spherical or spheroidal fillers, and the use of the fillers can lead to higher hardness of the adhesive, so that the technicians of the invention change the traditional thinking formula, change the spherical or spheroidal fillers into fibrous fillers, reduce the hardness of the polyurethane adhesive, greatly improve the bonding strength, and meet the requirements of shock absorption and bearing.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
One embodiment of the invention provides a polyurethane adhesive, which comprises a component A and a component B; the component B is isocyanate prepolymer; the component A comprises the following components in parts by weight: 5-65 parts of polyol, 0-1 part of chain extender, 1-3 parts of cross-linking agent, 15-40 parts of filler, 1-3 parts of rheological additive, 5-15 parts of water absorbent and 0.1-0.3 part of catalyst; wherein the polyol is at least one of polyether polyol and polyester polyol; the filler is fibrous filler.
In the process of research, the technicians of the invention find that the traditional adhesive generally adopts spherical or spheroidal fillers (such as the fillers with the length-diameter ratio of 5-20), and the use of the fillers can cause higher hardness of the adhesive, so the technicians of the invention change the traditional thinking formula, change the spherical or spheroidal fillers into fibrous fillers, reduce the hardness of the polyurethane adhesive, and greatly improve the bonding strength.
In one embodiment, the filler is a fibrous filler having an aspect ratio greater than 100.
In one embodiment, the filler is at least one of glass fibers and calcium sulfate whiskers.
In one embodiment, the filler is at least one of glass fibers produced by san Jose, Dongxin, and calcium sulfate whiskers produced by rain, Shandongxin.
In one embodiment, the polyol comprises at least a polyester polyol.
In one embodiment, the polyol is a combination of a polyester polyol and a polyether polyol; further, the mass ratio of the polyester polyol to the polyether polyol is (1-2): 1.
in one embodiment, in the component A, the polyether polyol is 2-25 parts, and the polyester polyol is 5-30.5 parts.
In one embodiment, the polyether polyol is a silicone oil-modified polyether polyol.
In one embodiment, the polyether polyol is at least one of A-600 produced by eastern Shandong Lanxingdong, Sovermol 760, 805, 810, 815 produced by German Basff and bisphenol A-polyoxyethylene ether produced by Tianmen Gangchang chemical industry;
in one embodiment, the polyester polyol is at least one of Span 20 produced by the Shanghai Minkoch chemical industry and PCL-2053, 2055 produced by the polyprenification chemical industry.
In one embodiment, in the component A, 0.1-0.8 part of chain extender is used; further, 0.5-0.8 part of chain extender.
In one embodiment, the chain extender has a structure represented by formula (I):
R1-R10each independently is H or C1-4An alkyl group; and R is1-R10At least one of them is C1-4An alkyl group;
a. b and c are each independently 0, 1 or 2.
The inventor of the present invention found in research that the chain extender having the structure shown in formula (I) can ensure lower hardness and higher adhesion strength of the colloid formed after curing, compared with the conventional unsubstituted diol chain extender (such as 1, 4-butanediol, 1, 3-propanediol, etc.).
Understandably, "R1-R10At least one of them is C1-4By alkyl is meant that the chain extender contains at least one C in addition to the hydroxyl substituents at both ends1-4Alkyl substituent, in this caseAnd the C1-4The carbon-corresponding units a, b and/or c of the alkyl radical being other than 0, e.g. R3Is C1-4Alkyl, in which case a is not 0.
It is understood that when a, b or c in the chain extender having the structure shown in formula (I) is 0, the carbon at the corresponding position is not present, for example: when a is 0, b is 0 and c is 0, the chain extender having the structure represented by the above formula (I) corresponds to a chain extender having a structure represented by the following formula (I)
The structure of (1); for example, when a is 0 and b and c are 1, the chain extender having the structure represented by the above formula (I) corresponds to a chain extender having a structure represented by the following formula (I)
The structure of (1).
When a, b or c is 2, it means that two carbons are connected by a single bond, and the substituents on the two carbons may be the same or different, for example: a is 2, b and c are 1, and the chain extender having the structure represented by the above formula (I) corresponds to a chain extender having a structure represented by the following formula (I)
Wherein two R are3Which may be the same or different from each other, two R4May be the same as or different from each other.
In one embodiment, a, b, and c are each independently 0 or 1.
In one embodiment, R1-R10Each independently is: H. methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl, and R1-R10At least one is not H.
In one embodiment, the chain extender is an asymmetric chain extender.
In one embodiment, R1And R2In which one substituent is present with R9Is different from R10Are also different, and/or; r3And R4In which one substituent is present with R7Is different from R8And are also different.
By adopting the chain extender with the asymmetric structure, compared with the colloid formed by the traditional symmetric chain extender, the technical personnel of the invention have higher bonding strength and can not obviously improve the hardness of the colloid.
In one embodiment, the chain extender is at least one of 3, 3-dimethyl-1, 2-butanediol, 2-n-butyl-1, 3-propanediol, 3-methyl-1, 3-butanediol, and 2-methyl-2, 4-pentanediol.
In one embodiment, the catalyst is a water inhibited reaction type catalyst.
In the research of the present inventors, it was found that in the conventional polyurethane adhesive, the catalyst is generally organic metal and amine, which can catalyze the main reaction (isocyanate and alcohol) and the side reaction of isocyanate and water, so it is necessary to reduce the water content in the system. The water content in the system can be reduced to a certain extent by adding the water absorbent into the system, and meanwhile, the water reaction inhibiting catalyst is added, so that the side reaction can be effectively avoided under the synergistic effect of the water absorbent and the water reaction inhibiting catalyst, the adhesive strength of the colloid formed by the polyurethane adhesive is further improved, and the influence on the hardness is small.
In one embodiment, the catalyst is one or more of Amicure KT-22, CuCat-HAA and CuCat-HAB; furthermore, the catalyst is at least one of Amicure KT-22 produced by winning-creating chemistry and CuCat-HAA and CuCat-HAB produced by Guangzhou Youyn chemistry.
In one embodiment, the water absorbent is at least one of calcium oxide and molecular sieve.
In one embodiment, the catalyst is present in an amount of 0.12 to 0.2 parts in component A.
In one embodiment, the cross-linking agent is at least one of glycerol, triethanolamine, and G-12, G-18, and G-25 of Jiangsu Haian petrochemical production.
In one embodiment, the rheological aid is at least one of R-974, R-812, manufactured by Woodbis chemical company, Germany, and H-20, manufactured by Wake chemical company, Inc.
In one embodiment, the reaction raw materials of the B component comprise: 300 parts of polypropylene glycol 1000(PPG-1000), 250-300 parts of carbodiimide modified 44 diphenylmethane diisocyanate (MDI-LL) and 0.01-0.05 part of catalyst.
In one embodiment, the catalyst in the component B is SD-L-101 produced by Jilin Huaxin chemical industry.
In one embodiment, the component B has 8 to 12% NCO (titration by di-n-butylamine method), an apparent density of 1.1 to 1.2g/ml (25 ℃), and a viscosity of 20000 to 50000cps (25 ℃).
In one embodiment, the component B is prepared by the following method:
(1) stirring the PPG-1000 for 1-3h at the temperature of 110-130 ℃ and the vacuum degree of-0.05-0.1 MPa;
(2) cooling to 15-45 ℃, adding carbodiimide modified 44 diphenylmethane diisocyanate, and reacting for 8-16h in an inert gas atmosphere;
(3) adding a catalyst, stirring for 1-3h at 45-55 ℃, reacting for 1-3h at 70-90 ℃ under the vacuum degree of-0.05-0.1 MPa, and obtaining the component B after the reaction is completed.
The invention also provides a colloid which is prepared by mixing and curing the component A and the component B in the polyurethane adhesive.
In one embodiment, the mixing ratio of the A component and the B component in the mixing of the A component and the B component is calculated by the molar ratio of OH in the A component to NCO in the B component being 1 (1.04-1.08). The implementation method of the invention also provides a preparation method of the colloid, which comprises the following steps:
s100: providing a polyurethane adhesive;
further, in step S100, the component a of the polyurethane adhesive can be prepared by the following method:
s1011: pretreating the polyalcohol and the chain extender of the component A;
in an embodiment, the preprocessing method in step S1011 includes: adding polyalcohol and chain extender into a reaction kettle, and stirring for 1-3h (preferably 2h) at the temperature of 110-130 ℃ (preferably 115-125 ℃) and under the vacuum degree of-0.05-0.1 MPa (preferably-0.08-0.1 MPa); cooling under inert gas atmosphere for use.
S1012: pretreating the filler;
in an embodiment, the preprocessing method of step S1012 is: and (3) baking the filler at the temperature of 140-160 ℃, and cooling for later use after baking is finished.
S1013: the raw materials pretreated in the steps S1011 and S1012 and the rest raw materials are uniformly mixed to prepare the component A.
Further, in step S1013, the raw materials to be mixed are put into a sample tank, simply stirred, and then put into a homogenizer to be mixed, and the raw materials are first mixed at 1500rpm for a predetermined time and then at 1800rpm for a predetermined time.
Further, in step S100, the component B of the polyurethane adhesive can be prepared by the following method:
s1021: stirring the PPG-1000 for 1-3h at the temperature of 110-130 ℃ and the vacuum degree of-0.05-0.1 MPa;
s1022: cooling to 15-45 ℃, adding carbodiimide modified 44 diphenylmethane diisocyanate, and reacting for 8-16h in an inert gas atmosphere;
s1023: adding a catalyst, stirring for 1-3h at 45-55 ℃, reacting for 1-3h at 70-90 ℃ under the vacuum degree of-0.05-0.1 MPa, and obtaining the component B after the reaction is completed.
S200: mixing the component A and the component B to prepare mixed slurry;
further, in step S200, the ratio of the component a to the component B in terms of mole ratio OH: NCO ═ 1 (1.04 to 1.08) is preferably 1:1.06 the calculated amounts were mixed.
S300: and coating the mixed slurry on the part to be pasted, and curing to obtain the colloid.
The colloid obtained by the preparation method has lower hardness and higher bonding strength, and is particularly suitable for application scenes needing shock absorption and load bearing, such as fixing of vehicle seats, fixing of battery cells and the like.
An embodiment of the invention also provides the application of the polyurethane adhesive in the preparation of vehicle seats and batteries.
The present invention will be described below with reference to specific examples.
In the following examples, the modified polyether polyol is Sovermol 815, produced by Pasteur, Germany; the polyester polyol is PCL-2053 produced by a polyester kernel chemical industry, the cross-linking agent is triethanolamine, the fibrous filler is calcium sulfate whisker produced by Shandongxin deluging, the rheological aid is R-974 produced by Yingchugsai, the water absorbent is calcium oxide produced by Hunan adult calcium industry, the water reaction inhibition type catalyst is CuCat-HAA produced by Guangzhou Youngun chemical industry, PPG-1000 Nanjing Boben, MDI-LL Korea brocade lake corporation, SD-L-101 Jilin Huaxin chemical industry, and the unspecified reagent is a conventional commercially available reagent.
Example 1
The A component of the polyurethane adhesive is as follows: 15 parts of modified polyether polyol, 15 parts of polyester polyol, 0.8 part of 2-methyl-2, 4-pentanediol, 1.6 parts of cross-linking agent, 29.6 parts of fibrous filler, 2.4 parts of rheological additive, 8.9 parts of water absorbent and 0.16 part of water reaction inhibition type catalyst, and the concrete contents are shown in Table 1;
and B component: PPG-1000200 parts, MDI-LL270 parts and SD-L-1010.012 parts.
The preparation method comprises the following steps:
(1) preparation of component A:
adding the polyol and the chain extender into a reaction kettle, and stirring for 2 hours under vacuum (-0.09MPa) at the temperature of 120 ℃; vacuum is removed by nitrogen, the mixture is cooled to room temperature and then subpackaged by an iron can, and the nitrogen is sealed for standby. Uniformly spreading the fibrous filler into an open vessel, putting the vessel containing the raw materials into a blast oven, baking for 4 hours at 150 ℃, taking out the vessel to a dryer, cooling to normal temperature, and packaging with an aluminum plastic film for later use.
Mixing the pretreated raw materials with the rest raw materials, manually stirring, mixing in a non-intrusive material homogenizer produced by Cizhen Utility science and technology Limited, at a rotation speed of 1500rpm for 2min each time for 1 time, and at a rotation speed of 1800rpm for 2min each time for 4 times to obtain component A.
(2) Preparation of the component B:
putting 300 parts of PPG-1000 produced by Nanjing Boben into a reaction kettle, stirring for 2 hours at 120 ℃ in vacuum (-0.09MPa), introducing nitrogen to normal pressure, and naturally cooling to room temperature; 270 parts of MDI-LL from Korea brocade lake corporation was added thereto, and the mixture was stirred and reacted at 35 ℃ under normal pressure and nitrogen atmosphere for 12 hours; adding 0.012 part of SD-L-101 produced in Jilin Huaxin chemical industry, and stirring and reacting for 2 hours under normal pressure and nitrogen atmosphere at 50 ℃; then stirred and reacted for 2 hours under the condition of 80 ℃ and vacuum (-0.09 MPa). The component B is a light yellow clear transparent liquid, NCO percent is 8.3 percent (titration by a di-n-butylamine method), the apparent density is 1.12g/ml (25 ℃), and the viscosity is 32000cps (25 ℃).
(3) By the molar ratio OH: calculating the mixing ratio of the component A and the component B according to NCO of 1:1.06, and mixing the component A and the component B to obtain mixed slurry;
(4) the mixed slurry was coated on a substrate and cured at 80 ℃ for 48 hours.
Example 2 to example 5
The A component of the polyurethane adhesive is as follows: see table 1;
and B component: same as example 1
The preparation method comprises the following steps: the difference from example 1 is that the A component is different.
TABLE 1
| Formulation of | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Modified polyether polyol | 15 | 25 | 0 | 15 | 15 |
| Polyester polyols | 12.2 | 0 | 30.5 | 12.2 | 12.2 |
| 3-methyl-1, 3-butanediol | 0 | 0 | 0 | 0.8 | 0 |
| 2-methyl-2, 4-pentanediol | 0.8 | 0.8 | 0.8 | 0 | 0 |
| Crosslinking agent | 1.6 | 1.6 | 1.6 | 1.6 | 1.6 |
| Fibrous filler | 29.6 | 27.4 | 32.8 | 29.6 | 28.8 |
| Rheology aid | 2.4 | 2.2 | 2.6 | 2.4 | 2.3 |
| Water absorbent | 8.9 | 8.2 | 9.9 | 8.9 | 8.6 |
| Water reaction inhibiting catalyst | 0.16 | 0.16 | 0.17 | 0.16 | 0.16 |
| Appearance of the A component after mixing | White paste | White paste | White paste | White paste | White paste |
Example 6-example 11
The A component of the polyurethane adhesive is as follows: see table 2;
and B component: same as example 1
The preparation method comprises the following steps: the difference from example 1 is that the A component is different.
TABLE 2
| Example 6 | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | |
| Modified polyether polyol | 15 | 15 | 15 | 15 | 15 | 15 |
| Polyester polyols | 12.2 | 12.2 | 12.2 | 12.2 | 12.2 | 12.2 |
| 1, 4-butanediol | 0.8 | 0 | 0 | 0 | 0 | 0 |
| 1, 3-butanediol | 0 | 0.8 | 0 | 0 | 0 | 0 |
| 2-methyl-2, 4-pentanediol | 0 | 0 | 0.8 | 0.8 | 0.8 | 0.8 |
| Crosslinking agent | 1.6 | 1.6 | 1.6 | 1.6 | 1.6 | 1.6 |
| Fibrous filler | 29.6 | 29.6 | 29.6 | 29.6 | 29.6 | 29.6 |
| Rheology aid | 2.4 | 2.4 | 2.4 | 2.4 | 2.4 | 2.4 |
| Water absorbent | 8.9 | 8.9 | 8.9 | 8.9 | 8.9 | 8.9 |
| Organotin catalysts | 0 | 0 | 0.04 | 0 | 0 | 0 |
| Water reaction inhibiting catalyst | 0.16 | 0.16 | 0 | 0.04 | 0.08 | 0.12 |
| Appearance of the A component after mixing | White paste | White paste | White paste | White paste | White paste | White paste |
Comparative examples 1 to 4
The A component of the polyurethane adhesive is as follows: see table 3;
and B component: same as example 1
The preparation method comprises the following steps: the difference from example 1 is that the A component is different.
TABLE 3
Performance testing
The tensile shear strength of the aluminum sheet-aluminum sheet is tested by referring to GB/T7124-2008 test of tensile shear strength of adhesive (rigid material to rigid material); reference is made to GB/T531.1-2008 "vulcanized rubber or thermoplastic rubber indentation hardness test method part I: shore Durometer method (Shore hardness) tests the hardness of the gel. In order to ensure complete curing of the adhesive, all comparative examples were cured at 80 ℃ for 48 hours, and the test results are shown in tables 4 to 6.
TABLE 4
TABLE 5
TABLE 6
As can be seen from tables 4 and 5, the polyurethane adhesives of examples 1 to 8 formed gels having lower hardness and higher adhesive strength.
In addition, it can be seen from comparing example 1, example 2 and example 3 that, although the adhesive strength of example 2 containing only polyether polyol is higher than that of example 1 in which polyether polyol and polyester polyol are combined, the colloidal hardness of example 2 is greatly improved; although the colloidal hardness of example 3 containing only a polyester polyol is lower than that of example 1 in which a polyether polyol and a polyester polyol are combined, the adhesive strength of example 3 is low. The system of the invention adopts the polyol formed by combining polyether polyol and polyester polyol, so that the traditional technical problem can be overcome, and the aim of reducing the hardness of colloid while ensuring the bonding strength is fulfilled.
Example 1, example 4, and example 5 were compared, except that the chain extender of example 1 was 2-methyl-2, 4-pentanediol, the chain extender of example 4 was 3-methyl-1, 3-butanediol, and the chain extender was not included in example 5. As can be seen from table 4, the effects of examples 1 and 4 are better than those of example 5, which shows that the presence of the chain extender can improve the adhesive strength of the colloid while ensuring that the colloid has lower hardness.
Example 1 was compared with examples 6 and 7 except that the chain extender of example 1 was 2-methyl-2, 4-pentanediol, the chain extender of example 6 was 1, 4-butanediol, and the chain extender of example 7 was 1, 3-butanediol. As can be seen from tables 4 and 5, the adhesive strength of examples 6 and 7 is significantly lower than that of example 1, which shows that the adhesive strength of the colloid can be significantly improved by using the asymmetric chain extender compared to the symmetric chain extender.
Comparing example 1 with example 8, except that example 1 is a water reaction-inhibited catalyst and example 8 is an organotin catalyst, it can be seen from tables 4 and 5 that the adhesive strength of example 8 is significantly lower than that of example 1. The application of the water reaction inhibiting catalyst can ensure that the colloid has lower hardness and improve the adhesive strength of the colloid.
Comparative example 1, example 9, example 10 and example 11, except that the content of the water reaction type catalyst was suppressed. As can be seen from tables 4 and 5, the amount of the water reaction type catalyst to be inhibited has an influence on the colloidal properties, and the amount of the water reaction type catalyst to be inhibited is preferably 0.12 to 0.16 part.
Comparative example 1, comparative example 2, comparative example 3 and comparative example 4, with the difference that comparative example 1 contains no filler, comparative examples 2 to 4 are various spherical or spheroidal fillers, specifically the filler of comparative example 2 is ultrafine calcium carbonate (800 mesh), the filler of comparative example 3 is wollastonite-1 (aspect ratio 5-10), and the filler of comparative example 4 is wollastonite-2 (aspect ratio 15-20). As can be seen from tables 4 and 6, comparative examples 1 to 4 are inferior to example 1 in both of the colloidal hardness and the adhesive strength of the colloid. The fibrous filler can effectively reduce the colloid hardness and improve the bonding strength so as to simultaneously meet the requirements of shock absorption and bearing.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A polyurethane adhesive is characterized by comprising a component A and a component B; the component B is isocyanate prepolymer;
the component A comprises the following components in parts by weight:
wherein the polyol is at least one of polyether polyol and polyester polyol;
the filler is fibrous filler.
2. The polyurethane adhesive of claim 1, wherein the polyol is a combination of a polyester polyol and a polyether polyol; and/or
The filler is at least one of glass fiber and calcium sulfate whisker.
3. The polyurethane adhesive of claim 1, wherein in the component A, the chain extender is 0.1-0.8 part, and the chain extender has a structure shown in formula (I):
R1-R10each independently is H or C1-4An alkyl group; and R is1-R10At least one of them is C1-4An alkyl group;
a. b and c are each independently 0, 1 or 2.
4. The polyurethane adhesive of claim 3, wherein R is1And R2In which one substituent is present with R9Is different from R10Are also different, and/or;
R3and R4In which one substituent is present with R7Is different from R8And are also different.
5. The polyurethane adhesive of claim 3, wherein the chain extender is at least one of 3, 3-dimethyl-1, 2-butanediol, 2-n-butyl-1, 3-propanediol, 3-methyl-1, 3-butanediol, and 2-methyl-2, 4-pentanediol.
6. The polyurethane adhesive of claim 1, wherein the catalyst is a water-inhibited reaction type catalyst, preferably the catalyst is one or more of Amicure KT-22, CuCat-HAA, and CuCat-HAB; and/or
The water absorbent is at least one of calcium oxide and molecular sieve.
7. The polyurethane adhesive of claim 1, wherein the polyether polyol is at least one of A-600 produced by eastern Lanzhong, Sovermol 760, 805, 810, 815 produced by German Basff, and bisphenol A-polyoxyethylene ether produced by Tianmen Gangchang chemical industry; and/or
The polyester polyol is at least one of Span 20 produced by Shanghai Minkou chemical industry and PCL-2053 and 2055 produced by polymer kernel chemical industry; and/or
The cross-linking agent is at least one of glycerol, triethanolamine and G-12, G-18 and G-25 in petrochemical production of Jiangsu Haian; and/or
The rheological additive is at least one of R-974 and R-812 produced by Woodbis sp and H-20 produced by Wake chemical Co.
8. The polyurethane adhesive of any one of claims 1-7, wherein the B component is prepared from the following raw materials:
1000300 parts of polypropylene glycol
250-300 parts of carbodiimide-modified 44 diphenylmethane diisocyanate
0.01-0.05 part of catalyst.
9. A gel obtained by mixing the A-component and the B-component in the polyurethane adhesive according to any one of claims 1 to 8 and curing the mixture.
10. The colloid of claim 9, wherein the mixing ratio of the A component and the B component in the mixing of the A component and the B component is calculated by the molar ratio of OH in the A component to NCO in the B component being 1 (1.04-1.08).
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| CN115612050A (en) * | 2022-12-19 | 2023-01-17 | 北京市政路桥管理养护集团有限公司 | Water plugging grouting material and preparation method thereof |
| CN115820191A (en) * | 2022-09-28 | 2023-03-21 | 上海安彼太新材料有限公司 | Two-component polyurethane structural adhesive for high-elasticity bonding of power battery |
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