WO2024124372A1 - 聚氨酯胶黏剂、无醛添加模压托盘及其制备方法 - Google Patents
聚氨酯胶黏剂、无醛添加模压托盘及其制备方法 Download PDFInfo
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- WO2024124372A1 WO2024124372A1 PCT/CN2022/138349 CN2022138349W WO2024124372A1 WO 2024124372 A1 WO2024124372 A1 WO 2024124372A1 CN 2022138349 W CN2022138349 W CN 2022138349W WO 2024124372 A1 WO2024124372 A1 WO 2024124372A1
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- polyurethane adhesive
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- 239000000853 adhesive Substances 0.000 title claims abstract description 77
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 77
- 239000004814 polyurethane Substances 0.000 title claims abstract description 71
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229920005862 polyol Polymers 0.000 claims abstract description 45
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 claims abstract description 39
- 150000003077 polyols Chemical class 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- -1 poly(ethylene oxide-propylene oxide) Polymers 0.000 claims abstract description 27
- 239000012948 isocyanate Substances 0.000 claims abstract description 26
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 26
- 229940126062 Compound A Drugs 0.000 claims abstract description 24
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 24
- 229920000570 polyether Polymers 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 36
- 239000002023 wood Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 20
- 238000007731 hot pressing Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 10
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- 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 3
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 1
- 101100020663 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) ppm-1 gene Proteins 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 24
- 238000003825 pressing Methods 0.000 abstract 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 12
- 235000017491 Bambusa tulda Nutrition 0.000 description 12
- 241001330002 Bambuseae Species 0.000 description 12
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 12
- 239000011425 bamboo Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
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- 238000012360 testing method Methods 0.000 description 7
- 238000004026 adhesive bonding Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000012805 post-processing Methods 0.000 description 6
- 238000004513 sizing Methods 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 235000017060 Arachis glabrata Nutrition 0.000 description 4
- 244000105624 Arachis hypogaea Species 0.000 description 4
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- 230000009286 beneficial effect Effects 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 235000020232 peanut Nutrition 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000010902 straw Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 101000972853 Hordeum vulgare Non-specific lipid-transfer protein 3 Proteins 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 241000219000 Populus Species 0.000 description 2
- 229920002522 Wood fibre Polymers 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002025 wood fiber Substances 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 102000011759 adducin Human genes 0.000 description 1
- 108010076723 adducin Proteins 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Definitions
- the invention relates to the technical field of adhesives for molded products, in particular molded pallets, and in particular to a polyurethane adhesive particularly suitable for molded pallets and an application thereof.
- Molded pallets are made of wood, straw, peanut shells, cotton stalks, and bamboo. After being crushed, cut into shavings, dried, and applied with a certain adhesive, they are molded at high temperature and high pressure in one go. Compared with large foreign manufacturers and a relatively complete shavings molded pallet system, domestic shavings molded pallets started late and developed slowly. At present, with the exception of a few domestic companies, most of them have an annual output of 200,000 pieces or less. There are few companies in the market that use polyurethane glue to prepare molded pallets, and they are immature.
- the invention patent with announcement number CN102336292A uses a mixture of isocyanate and urea glue or a mixture of phenolic resin and melamine to prepare molded pallets, but the glue still contains formaldehyde, which will continue to release formaldehyde during long-term storage of the pallets.
- the invention patent application with announcement number CN114058311A discloses a modified isocyanate adhesive and a preparation method thereof.
- the isocyanate is modified by benzene ring-containing siloxane and polyethylene glycol monomethyl ether to make the molecular chain have good flexibility, effectively improving the hydrophilicity, initial adhesion, and demolding performance.
- the invention patent with announcement number CN105881693A discloses a molded pallet and its manufacturing process.
- the main material and the auxiliary material are separated and crushed into granules, and isocyanate adhesive is selected.
- the molded pallet has better strength and stability than the existing technology.
- the present invention provides a polyurethane adhesive, a formaldehyde-free molded pallet and a preparation method thereof.
- the polyurethane adhesive provided by the present invention is particularly suitable for molded products, especially for use in formaldehyde-free molded pallets, which can significantly improve production efficiency and increase the mechanical strength of molded pallets.
- the present invention provides the following technical solutions:
- the present invention provides a polyurethane adhesive, which is obtained by reacting reaction raw materials including component I and component II;
- the polyether polyol is selected from one or more of polyoxyethylene polyol and polyoxyethylene-oxypropylene polyol;
- the compound A is selected from one or more of the compounds of the following structural formula (I) and structural formula (II):
- n in structural formula (I) and structural formula (II) is independently an integer of 1-5, for example, n is 1, 2, 3, 4 or 5.
- the polyurethane adhesive prepared by using the above-mentioned component I (including isocyanate) and component II (including polyoxyethylene polyol and/or polyoxyethylene-propylene oxide polyol, and a specific compound A) is applied to the preparation process of molded products such as molded pallets, has a good application effect, is beneficial to improving production efficiency and the mechanical properties of the product, can achieve compression molding within a relatively short holding time, and can give the product a higher bonding strength.
- compound A is selected from one or more compounds of structural formula (II).
- compounds of structural formula (II) in component II have more outstanding performance in improving the production efficiency of molded pallets, are conducive to improving the production efficiency of products with excellent mechanical properties, and can significantly shorten the holding time required for pallet compression molding.
- compound A in component II is combined with specific polyether polyols and isocyanates to obtain molded products with excellent mechanical properties, especially molded pallets, with high production efficiency.
- the mass content of compound A in component II can be 1ppm-1%, for example, 1ppm, 5ppm, 10ppm, 50ppm, 100ppm, 200ppm, 300ppm, 400ppm, 500ppm, 0.5%, 1%, etc., preferably 1-500ppm, for example 1-100ppm, etc.
- the sum of the amounts of the component I and the component II is 100 parts by mass:
- the amount of component I is 80-99 parts by mass, for example 80, 82, 85, 87, 90, 92, 95, 97, 99 parts by mass, etc., preferably 85-95 parts by mass;
- the amount of component II is 1-20 parts by mass, for example, 1, 3, 5, 8, 10, 13, 15, 18, 20 parts by mass, etc., preferably 3-10 parts by mass.
- the polyurethane adhesive prepared by using the above preferred mass ratio of component I and component II and applied to the molded product preparation process has a better application effect, which is conducive to further significantly improving the production efficiency and mechanical properties of the product.
- the molding can be achieved in a relatively shorter holding time, and the adhesive has good compatibility with the substrate material, especially the substrate material based on herbaceous plants or woody plants (such as wood or bamboo), and is easy to achieve a higher bonding strength.
- the polyether polyol can be selected from the corresponding raw materials conventionally used in the art, and there is no particular limitation on this.
- the polyether polyol is selected from one or more of polyoxyethylene polyols and polyoxyethylene-propylene oxide polyols having a molecular weight Mn of 1000-5000 g/mol and a functionality of 2-4, and is preferably selected from one or more of polyoxyethylene polyols and polyoxyethylene-propylene oxide polyols having a molecular weight Mn of 3000-5000 g/mol and a functionality of 2-4.
- the isocyanate can be selected from the corresponding raw materials conventionally used in the art, and there is no particular limitation on this.
- the functionality of the isocyanate is ⁇ 2, and is preferably selected from a combination of one or more of toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and polymethylene polyphenyl polyisocyanate.
- polymethylene polyphenyl polyisocyanate is, for example, but not limited to, Wannate series polyisocyanates of Wanhua Chemical Group Co., Ltd., including any one or a combination of at least two of PM-100, PM-200, PM-400, PM-600, PM-700, CW20, and CW30.
- component II of the present invention compound A can be included in component II by adding it separately, or it can be provided in a way that it is provided as a whole with the polyether polyol raw material.
- component II of the present invention can be provided in the form of a polyether polyol containing the required amount of compound A in advance.
- the content of compound A in component II of the present invention can be determined by a conventional content determination method in the art, for example, using a gas chromatography-mass spectrometer (GC-MS) according to the conventional method of the instrument to determine the content of compound A in component II.
- GC-MS gas chromatography-mass spectrometer
- the content of compound A in component II can be determined by referring to the following operation: take 30 mg of component II and place it in a sealed glass tube, place it in a thermal desorber of a gas chromatography-mass spectrometer (GC-MS), heat it at 90°C for 10 minutes, and automatically inject the sample for content detection.
- the present invention also provides a method for preparing the polyurethane adhesive described above, wherein the method comprises mixing various reaction raw materials to obtain the polyurethane adhesive.
- the reaction is carried out at 60-90°C, preferably 70-80°C, and the reaction time is preferably 1-4h, more preferably 1.5-2.5h; the stirring rate during the reaction is preferably 300-500rad/s, more preferably 300-400rad/s.
- the polyurethane adhesive provided by the present invention firstly improves the compatibility of isocyanate with water by reacting the isocyanate group with the hydroxyl group of polyethylene oxide polyol and/or polyethylene oxide-propylene oxide polyol, so that the residual isocyanate can react with water in a homogeneous phase, which greatly improves the reaction rate with water in the substrate material during the subsequent hot pressing process of molded products such as molded trays, and is more conducive to the molding of molded trays.
- double bonds are introduced into the polyurethane adhesive system by reacting the isocyanate group with compound A of structural formula (I) and/or (II); since common substrate materials, especially substrate materials based on herbaceous plants and/or woody plants (such as wood or bamboo), contain a large amount of lignin, cellulose (rich in double bonds), etc., the compatibility with the substrate material can be effectively improved, thereby facilitating the formation of a higher bonding strength; in addition, the ether structure in compound A is extremely compatible with the chain structure of the polyether polyol; under the combined effect of the above aspects, a strong bonding effect can be achieved in the preparation process of molded products, especially molded pallets, the production time can be reduced (i.e., the holding time), the production efficiency can be improved, and products with good mechanical properties can be obtained.
- the present invention also provides the use of the polyurethane adhesive described above in molded products.
- the polyurethane adhesive of the present invention is applied to molded products, which is beneficial to improving the preparation efficiency of molded products, shortening the holding time, and obtaining products with excellent mechanical properties.
- the molded products include one or more of molded sheet materials (such as plywood, fiberboard, particleboard, etc.) and molded pallets;
- the substrate material of the molded products can be those conventionally selected in the art, for example, the substrate material of the molded products can be but is not limited to one or more of shavings, boards, and fibers, preferably including shavings, boards, and fibers derived from herbaceous plants and woody plants, specifically for example one or more of wood shavings, wood boards, wood fibers, bamboo shavings, bamboo boards, bamboo fibers, peanut shells, straw, cotton stalks, etc.; in some embodiments, the substrate material of the molded products includes materials derived from agricultural and forestry residues.
- three agricultural and forestry residues includes, for example, logging residues, timber making residues, processing residues, etc.; logging residues include, for example, branches, twigs, treetops, bark, leaves, roots, vines, shrubs, etc. remaining in the logging process; timber making residues include, for example, timber making ends, etc.; processing residues include, for example, board skins, laths, wood and bamboo ends, sawdust, broken veneer, wood cores, shavings, wood blocks, leftover scraps, etc.
- the present invention also provides a formaldehyde-free molded pallet, wherein the adhesive used in the molded pallet is the polyurethane adhesive described above.
- the polyurethane adhesive of the present invention is particularly suitable for use in molded pallets, can effectively improve production efficiency, shorten the holding time, and can significantly improve the mechanical properties of molded pallets.
- the substrate material of the molded pallet can be those conventionally used in the art, such as but not limited to one or more of shavings, boards, and fibers, preferably including shavings, boards, and fibers derived from herbaceous plants and woody plants, specifically such as one or more of wood shavings, wood boards, wood fibers, bamboo shavings, bamboo boards, bamboo fibers, straw, peanut shells, and cotton stalks; in some embodiments, the substrate material of the molded product includes a material derived from agricultural and forestry residues.
- the amount of the polyurethane adhesive is 3%-10% of the mass of the substrate material, such as 3%, 5%, 7%, 10%, etc.
- the polyurethane adhesive of the present invention is applied according to the preferred amount, which is conducive to obtaining a molded pallet with better production efficiency and better performance.
- the present invention also provides a method for preparing the above-mentioned formaldehyde-free molded pallet, the preparation method comprising the following steps:
- the application method is, for example, atomization or spraying
- step 3 after completing step 3), the molded tray is taken out from the hot press, the edges are polished, and then cooled and stored.
- the hot pressing temperature is 120°C-200°C
- the holding pressure is 13-20Mpa
- the holding time is 80s-300s.
- the polyurethane adhesive of the present invention can be used to complete the hot pressing in a relatively shorter holding time, thereby improving production efficiency.
- the holding time can be shortened to 80s-250s, such as 80s-200s, such as lower than 200s, such as 80s, 100s, 120s, 150s, 170s, 180s, 200s, etc.
- the density of the obtained molded pallet is 800-1100 kg/m 3 , preferably 900-1000 kg/m 3 .
- the polyurethane adhesive provided by the present invention is prepared based on isocyanate, polyoxyethylene polyol and/or polyoxyethylene-propylene oxide polyol, and a specific compound A.
- the polyurethane adhesive is applied to molded products, especially molded pallets, and is beneficial to improving production efficiency and mechanical properties of molded products.
- Polyether polyol1 WANOL C3185, polyoxyethylene polyol, Wanhua Chemical Group Co., Ltd.
- Polyether polyol2 WANOL R2305, polyoxyethylene-oxypropylene polyol, Wanhua Chemical Group Co., Ltd.
- Polyether polyol 3 WANOL C3110, polyoxyethylene-oxypropylene polyol, Wanhua Chemical Group Co., Ltd.
- Isocyanate II 1:1 (mass ratio) mixture of WANNATE PM200 and WANNATE MDI-100, Wanhua Chemical Group Co., Ltd.
- Isocyanate III WANNATE HDI, Wanhua Chemical Group Co., Ltd.;
- Release agent 1 polyethylene wax type, HA-soft80, Jiangsu Haian Petrochemical Co., Ltd.;
- Release agent 2 silicone oil type, KC201, Wanhua Chemical Group Co., Ltd.
- Pallet mechanical testing machine PN-CT50KE, Hangzhou Pinxiang Technology Co., Ltd., is mainly used to test the pallet fork lifting performance and concentrated load on the plate surface;
- Embodiment 1 is a diagrammatic representation of Embodiment 1:
- the prepared polyurethane adhesive is used in the production of formaldehyde-free molded pallets.
- Gluing process polyurethane adhesive is applied to the wood shavings raw material by atomizing at a sizing amount of 10% (based on the mass of the wood shavings).
- Hot pressing process spray release agent 1 on each part of the upper and lower molds of the hot press. After the release agent has no volatile matter and forms a film on the upper and lower molds, place the wood chips applied with polyurethane adhesive in the mold, flatten it and hot press it at 174°C. The holding time is 150s and the holding pressure is 18Mpa.
- Post-processing step After the molded tray is taken out of the hot press, the edges are polished and cooled and stored.
- Embodiment 2 is a diagrammatic representation of Embodiment 1:
- the prepared polyurethane adhesive is used in the production of formaldehyde-free molded pallets.
- Raw material preparation Pine wood shavings are obtained by chipping and slicing, and the moisture content of the shavings is controlled to be 20wt% after drying.
- Gluing process polyurethane adhesive is applied to the wood shavings by pouring glue at a sizing amount of 7% (based on the mass of wood shavings).
- Hot pressing process spray release agent 2 on each part of the upper and lower molds of the hot press. After the release agent has no volatile matter and forms a film on the upper and lower molds, place the wood chips applied with polyurethane adhesive in the mold, flatten it and hot press it at 200°C. The holding time is 140s and the holding pressure is 14Mpa.
- Post-processing step After the molded tray is taken out of the hot press, the edges are polished and cooled and stored.
- Embodiment 3 is a diagrammatic representation of Embodiment 3
- the prepared polyurethane adhesive is used in the production of formaldehyde-free molded pallets.
- Raw material preparation bamboo raw material shavings are obtained by chipping and slicing, and the moisture content of the shavings is controlled to be 10wt% after drying.
- Gluing process The polyurethane adhesive is applied to the wood shavings raw material by atomizing at a sizing amount of 4% (based on the mass of the wood shavings).
- Hot pressing process spray release agent 1 on each part of the upper and lower molds of the hot press. After the release agent has no volatile matter and forms a film on the upper and lower molds, place the wood chips applied with polyurethane adhesive in the mold, flatten it and hot press it at 143°C. The holding time is 100s and the holding pressure is 16Mpa.
- Post-processing step After the molded tray is taken out of the hot press, the edges are polished and cooled and stored.
- Embodiment 4 is a diagrammatic representation of Embodiment 4:
- the prepared polyurethane adhesive is used in the production of formaldehyde-free molded pallets.
- Raw material preparation peanut shell raw material shavings are obtained by chipping and shaving, and the moisture content of the shavings is controlled to be 15wt% after drying.
- Gluing process polyurethane adhesive is applied to the wood shavings raw material by pouring glue at a sizing amount of 5% (based on the mass of wood shavings).
- Hot pressing process spray release agent 1 on each part of the upper and lower molds of the hot press. After the release agent has no volatile matter and forms a film on the upper and lower molds, place the wood chips applied with polyurethane adhesive in the mold, flatten it and hot press it at 196°C. The holding time is 90s and the holding pressure is 13Mpa.
- Post-processing step After the molded tray is taken out of the hot press, the edges are polished and cooled and stored.
- Embodiment 5 is a diagrammatic representation of Embodiment 5:
- the prepared polyurethane adhesive is used in the production of formaldehyde-free molded pallets.
- Raw material preparation Poplar wood shavings are obtained by chipping and slicing, and the moisture content of the shavings is controlled to be 8wt% after drying.
- Gluing process polyurethane adhesive is applied to the wood shavings raw material by atomizing at a sizing amount of 3% (based on the mass of the wood shavings).
- Hot pressing process spray release agent 2 on each part of the upper and lower molds of the hot press. After the release agent has no volatile matter and forms a film on the upper and lower molds, place the wood chips applied with polyurethane adhesive in the mold, flatten it and hot press it at 164°C. The holding time is 80s and the holding pressure is 16Mpa.
- Post-processing step After the molded tray is taken out of the hot press, the edges are polished and cooled and stored.
- Embodiment 6 is a diagrammatic representation of Embodiment 6
- the prepared polyurethane adhesive is used in the production of formaldehyde-free molded pallets.
- Raw material preparation Pine wood shavings are obtained by chipping and slicing, and the moisture content of the shavings is controlled to be 17 wt % after drying.
- Gluing process polyurethane adhesive is applied to the wood shavings raw material by atomizing at a sizing amount of 8% (based on the mass of the wood shavings).
- Hot pressing process spray release agent 1 on each part of the upper and lower molds of the hot press. After the release agent has no volatile matter and forms a film on the upper and lower molds, place the wood chips applied with polyurethane adhesive in the mold, flatten it and hot press it at 120°C, with a holding time of 160s and a holding pressure of 20Mpa.
- Post-processing step After the molded tray is taken out of the hot press, the edges are polished and cooled and stored.
- the component II in step S1 does not contain compound a5;
- the holding time in step SS3 is 250 s.
- step S1 no polyether polyol is used
- step SS3 the holding time is 300 s.
- step S1 No isocyanate is used in step S1;
- step SS3 the holding time is 400 s.
- step S1 compound a3 is used instead of compound a5;
- the holding time in step SS3 is 230 s.
- the polyurethane adhesive prepared by reacting isocyanate, polyether polyol and compound A in combination can greatly shorten the holding time required for hot pressing of the pallet compared to comparative documents 1 and 2, greatly improve the production efficiency, and significantly improve the mechanical properties of the molded pallet.
- Example 4 when using allyl ether with an n value greater than 5, under process conditions basically the same as those in Example 4, a longer holding time is required to achieve compression molding of the tray, the production efficiency is greatly reduced, and the comprehensive mechanical properties are also significantly inferior to those of the embodiment.
- the compound A containing structural formula (II) in component II can achieve compression molding of the tray within a shorter holding time than the compound A containing structural formula (I), and can further significantly improve production efficiency while taking into account excellent product mechanical properties.
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- Adhesives Or Adhesive Processes (AREA)
Abstract
本发明提供一种聚氨酯胶黏剂、无醛添加模压托盘及其制备方法，涉及模压托盘的胶黏剂技术领域。本发明提供的聚氨酯胶黏剂特别适用于模压制品，尤其是在无醛添加模压托盘中应用，能够显著改善生产效率和提高模压托盘的力学强度。所述聚氨酯胶黏剂采用包括组分I和组分II的反应原料经反应获得；其中，所述组分I包括异氰酸酯；所述组分II包括聚醚多元醇和化合物A；所述聚醚多元醇选自聚氧化乙烯多元醇、聚氧化乙烯-氧化丙烯多元醇中的一种或多种；所述化合物A选自如下结构式(I)和结构式(II)的化合物中的一种或多种：其中，结构式(I)和结构式(II)中的n独立地为1-5的整数。
Description
本发明涉及模压制品特别是模压托盘的胶黏剂技术领域，具体涉及一种特别适用于模压托盘的聚氨酯胶黏剂及其应用。
随着全球包装行业的快速发展，2020年世界包装产业总规模达10739亿，中国取代美国成为全球最大的包装市场。托盘作为重要的包装形式，在现代物流中有着不可替代的作用。目前国内对物流行业降本增效的要求越发迫切，模压托盘作为一种物美价廉、高效实用的产品能满足码头、货场、仓库、车间、商场等地的搬运、储存等需要。
模压托盘是以木材、秸秆、花生壳、棉杆、竹材为原料，经过破碎、切削成刨花、干燥并施加一定胶黏剂后，高温高压一次性模压成型的新型产品。相对于国外大型生产商及较为完善的刨花模压托盘体系，国内刨花模压托盘起步晚，发展慢。目前国内企业除个别外，大多数年产量在20万片及以下。市场以聚氨酯胶制备模压托盘企业较少，且不成熟。
公告号为CN102336292A的发明专利将异氰酸酯和脲胶混合物或者酚醛树脂和三聚氰胺的混合物用于制备模压托盘，但是胶液内仍含有甲醛，在托盘长期存放中仍会不断的释放甲醛。公告号为CN114058311A的发明专利申请公开了一种改性异氰酸酯胶粘剂及其制备方法，通过含苯环的硅氧烷和聚乙二醇单甲醚改性异氰酸酯，使分子链具有很好的柔韧性，有效改善了亲水性、初粘性、脱模性能。公告号为CN105881693A的发明专利公开了一种模压托盘及其制造工艺，将主料与辅料分开进行粉碎形成颗粒状，选用异氰酸脂胶黏剂，成型后的托盘相比现有技术有更好的强度与稳定性。
然而，关于如何基于聚氨酯胶来提升无醛添加模压托盘的生产效率及托盘性能的研究在现有技术中并无报道。
发明内容
有鉴于此，本发明提供一种聚氨酯胶黏剂、无醛添加模压托盘及其制备方法。本发明提供的聚氨酯胶黏剂特别适用于模压制品，尤其是在无醛添加模压托盘中应用，能够显著改善生产效率和提高模压托盘的力学强度。
本发明为达到其目的，提供如下技术方案：
本发明提供一种聚氨酯胶黏剂，所述聚氨酯胶黏剂采用包括组分I和组分II的反应原料经反应获得；
其中，所述组分I包括异氰酸酯；所述组分II包括聚醚多元醇和化合物A；
所述聚醚多元醇选自聚氧化乙烯多元醇、聚氧化乙烯-氧化丙烯多元醇中的一种或多种；
所述化合物A选自如下结构式(I)和结构式(II)的化合物中的一种或多种：
其中，结构式(I)和结构式(II)中的n独立地为1-5的整数，例如n取值为1、2、3、4或5。
采用上述组分I(包括异氰酸酯)、组分II(包括聚氧化乙烯多元醇和/或聚氧化乙烯-氧化丙烯多元醇、特定的化合物A)制备得到的聚氨酯胶黏剂，将其应用于模压制品例如模压托盘的制备工艺中，具有良好的应用效果，利于改善生产效率和产品的力学性能，能够在相对短的保压时间内实现模压成型，能够赋予产品较高的粘结强度。
较佳的，化合物A优选选自结构式(II)的化合物中的一种或多种。组分II中含有结构式(II)的化合物相比于含有结构式(I)的化合物，在提高模压托盘生产效率上，性能更加突出，利于提高获得力学性能优良的产品的生产效率，能显著缩短托盘模压成型所需的保压时间。
本发明的聚氨酯胶黏剂中，组分II中的化合物A配合特定的聚醚多元醇和异氰酸酯，可以以较高生产效率获得力学性能优异的模压制品特别是模压托盘，一些实施方式中，组分II中化合物A的质量含量可以为1ppm-1％，例如，1ppm、5ppm、10ppm、50ppm、100ppm、200ppm、300ppm、400ppm、500ppm、0.5％、1％等，优选1-500ppm，例如1-100ppm等。
优选实施方式中，以所述组分I、所述组分II的用量之和为100质量份计：
所述组分I的用量为80-99质量份，例如80、82、85、87、90、92、95、97、99质量份等，优选85-95质量份；
所述组分II的用量为1-20质量份，例如1、3、5、8、10、13、15、18、20质量份等，优选3-10质量份。
本发明人发现，基于采用上述优选的质量配比的组分I、组分II来制备聚氨酯胶黏剂，将其应用于模压制品制备工艺中，具有更佳的应用效果，利于进一步显著改善生产效率和产品的力学性能。能够在相对更短的保压时间内实现模压成型，且该胶粘剂与基材材料特别是基于草本植物或木本植物(例如木质或竹质)的基材材料具有良好的相容性，易于实现较高的粘结强度。
本发明的聚氨酯胶黏剂中，聚醚多元醇可以选择本领域常规使用的相应原料，对此没有特别限制，较佳的，所述聚醚多元醇选自分子量Mn为1000-5000g/mol且官能度2-4的聚氧化乙烯多元醇、聚氧化乙烯-氧化丙烯多元醇中的一种或多种，优选选自分子量Mn为3000-5000g/mol且官能度2-4的聚氧化乙烯多元醇、聚氧化乙烯-氧化丙烯多元醇中的一种或多种。
本发明的聚氨酯胶黏剂中，异氰酸酯可以选择本领域常规使用的相应原料，对此没有特别限制，较佳的，所述异氰酸酯的官能度≥2，优选选自甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯(HDI) 和异佛尔酮二异氰酸酯(IPDI)、多亚甲基多苯基多异氰酸酯中的一种或多种的组合。其中多亚甲基多苯基多异氰酸酯例如为但不限于万华化学集团股份有限公司的Wannate系列多异氰酸酯，包括PM-100、PM-200、PM-400、PM-600、PM-700、CW20及CW30中的任意一种或至少两种的组合。
本发明的组分II中，化合物A可以通过单独添加的方式包含在组分II中，也可以是与聚醚多元醇原料一体提供的方式来提供本发明的组分II，例如可以是以预先含有所需量的化合物A的聚醚多元醇的方式提供本发明的组分II。优选实施方式中，无论以何种方式提供组分II，基于组分II的总质量，其中化合物A的含量优选为1ppm-1％，更优选1-500ppm。在具体应用中，如有需要，对于本发明的组分II中化合物A的含量可通过本领域常规的含量测定方法来进行确定，例如采用气相色谱-质谱联用仪(GC-MS)按照该仪器的常规方法可以确定组分II中化合物A的含量。示例的，例如可以参照如下操作来确定组分II中化合物A的含量：取30mg组分II置于玻璃管中密封，将其放置于气相色谱-质谱联用仪(GC-MS)的热脱附仪中，在90℃下加热10分钟，自动进样进行含量检测。
本发明还提供上文所述的聚氨酯胶黏剂的制备方法，所述制备方法包括将各反应原料混合反应得到所述聚氨酯胶黏剂。
优选的，所述反应在60-90℃优选70-80℃下进行，反应时间优选为1-4h，更优选为1.5-2.5h；反应过程中进行搅拌的搅拌速率优选为300-500rad/s，更优选300-400rad/s。
本发明提供的聚氨酯胶黏剂，首先，通过异氰酸酯基团与聚氧化乙烯多元醇和/或聚氧化乙烯-氧化丙烯多元醇的羟基反应，提高异氰酸酯与水的相容性，使残余的异氰酸根能够在均相下与水反应，极大的提高了在后续模压制品例如模压托盘的热压过程中与基材材料中的水的反应速率，更加有利于模压托盘成型。其次，通过异氰酸酯基团与结构式(I)和/或(II)的化合物A反应，在聚氨酯胶黏剂体系中引入双键；由于常见的基材材料特别是基于草本植物和/或木本植物(例如木质或竹质)的基材材料中都有大量的木质素、 纤维素(丰富的双键)等，可以有效提升与基材材料的相容性，进而利于形成更高的粘接强度；除此以外，化合物A中醚建与聚醚多元醇的链段结构又存在极度相容性；在上述几方面综合作用下，可以在模压制品特别是模压托盘制备过程实现较强的粘接效果，降低生产时间(即保压时间)，提高生产效率，且获得力学性能良好的产品。
本发明还提供上文所述的聚氨酯胶黏剂在模压制品中的应用。本发明的聚氨酯胶黏剂应用于模压制品中，有利于改善模压制品的制备效率，缩短保压时间，并获得力学性能优异的产品。具体的，模压制品包括模压板材(例如胶合板、纤维板、刨花板等)和模压托盘中的一种或多种；模压制品的基材材料可以是本领域常规选择的那些，例如模压制品的基材材料可以为但不局限于刨花、板、纤维中的一种或多种，优选包括源于草本植物和木本植物的刨花、板、纤维，具体例如木质刨花、木质板、木质纤维、竹刨花、竹板、竹纤维、花生壳、秸秆、棉杆等中的一种或多种；一些实施方式中，模压制品的基材材料包括来源于农林三剩物的材料。关于农林三剩物的含义为本领域所熟知的，农林三剩物例如包括采伐剩余物，造材剩余物，加工剩余物等；采伐剩余物例如包括采伐过程中剩余的枝、丫、树梢、树皮、树叶、树根、藤条、灌木等，造材剩余物例如包括造材截头等，加工剩余物例如包括板皮、板条、木竹截头、锯沫、碎单板、木芯、刨花、木块、边角余料等。
本发明还提供一种无醛添加模压托盘，所述模压托盘中所用的胶黏剂为上文所述的聚氨酯胶黏剂。本发明的聚氨酯胶黏剂特别适用于在模压托盘中使用，能够有效提高生产效率，缩短保压时间，且能显著改善模压托盘的力学性能。模压托盘的基材材料可以为本领域常规使用的那些，例如包括但不限于刨花、板、纤维中的一种或多种，优选包括源于草本植物和木本植物的刨花、板、纤维，具体例如木质刨花、木质板、木质纤维、竹刨花、竹板、竹纤维、秸秆、花生壳、棉杆中的一种或多种；一些实施方式中，模压制品的基材材料包括来源于农林三剩物的材料。
较佳的，本发明的模压托盘中，所述聚氨酯胶黏剂的用量为所述基材材料质量的3％-10％，例如3％、5％、7％、10％等。本发明的聚氨酯胶黏剂按照 优选用量施加，利于获得兼顾较佳生产效率和较佳性能的模压托盘。
本发明还提供上文所述的无醛添加模压托盘的制备方法，所述制备方法包括如下步骤：
1)将所述基材材料的含水率控制在8-20wt％，例如8％、10％、15％、20％等；
2)将所述聚氨酯胶黏剂施加于所述基材材料上；施加方式例如为雾化施胶或淋胶；
3)在热压机的模具上施加脱模剂，然后将步骤2)得到的基材材料置于热压机的模具中，之后进行热压以形成所述模压托盘。脱模剂可以为本领域常见的脱模剂原料，脱模剂例如为但不限于聚乙烯蜡，硅油等，施加脱模剂的量以能在模具表面形成脱模剂膜层为准。
具体的，还可包括如下操作，在完成步骤3)后，将模压托盘从热压机中取出，将边部打磨后，冷却陈放。
较佳的实施方式中，步骤3)中，进行所述热压时，热压温度为120℃-200℃，保压压力为13-20Mpa，保压时间为80s-300s。采用本发明的聚氨酯胶黏剂可以在相对更短的保压时间内完成热压，从而提高生产效率，具体的，保压时间可缩短为80s-250s，例如为80s-200s，例如比200s更低，例如80s、100s、120s、150s、170s、180s、200s等。
一些实施方式中，所得到的模压托盘的密度在800-1100kg/m
3，优选900-1000kg/m
3。
本发明提供的技术方案具有如下有益效果：
本发明提供的聚氨酯胶黏剂，基于异氰酸酯、聚氧化乙烯多元醇和/或聚氧化乙烯-氧化丙烯多元醇、特定的化合物A来制备得到，该聚氨酯胶黏剂应用于模压制品特别是模压托盘中，有利于改善生产效率和模压产品的力学性能。
为了便于理解本发明，下面将结合实施例对本发明作进一步的说明。应当理解，下述实施例仅是为了更好的理解本发明，并不意味着本发明仅局限于以下实施例。
除非另有定义，本文所使用的所有的技术和科学术语与本发明所属技术领域的技术人员通常理解的含义相同。本文可能使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
实施例中未注明具体实验步骤或条件之处，可按照本技术领域中相应的常规实验步骤的操作或条件进行即可。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
以下实施例或对比例中所用的部分原料说明如下：
化合物a1：
上海迈瑞尔生化科技有限公司
化合物a2：
江苏海安石化有限公司；
化合物a3：
江苏海安石化有限公司；
化合物a4：
湖北实兴化工有限公司；
化合物a5：
Advanced Chemblocks公司；
化合物a6：
Advanced Chemblocks公司；
聚醚多元醇①：WANOL C3185，聚氧化乙烯多元醇,万华化学集团股份有限公司；
聚醚多元醇②：WANOL R2305，聚氧化乙烯-氧化丙烯多元醇，万华化学集团股份有限公司；
聚醚多元醇③：WANOL C3110，聚氧化乙烯-氧化丙烯多元醇，万华化学集团股份有限公司；
异氰酸酯Ⅰ：WANNATE CW20，万华化学集团股份有限公司；
异氰酸酯Ⅱ：WANNATE PM200与WANNATE MDI-100的1：1(质量比)混合物，万华化学集团股份有限公司；
异氰酸酯Ⅲ：WANNATE HDI，万华化学集团股份有限公司；
脱模剂1：聚乙烯蜡型，HA-soft80，江苏海安石化有限公司；
脱模剂2：硅油型，KC201，万华化学集团股份有限公司。
实施例中测试使用的主要实验仪器：
托盘力学试验机，PN-CT50KE，杭州品享科技有限公司，主要用于测试托盘叉举性能和板面集中载荷；
万能力学试验机，A1-7000H，高铁检测仪器(东莞)有限公司，主要用于测试托盘内结合强度、加强筋抗弯强度和支撑腿抗压强度；
实施例1：
制备聚氨酯胶黏剂：
S1：在装有搅拌器、温度计的5L反应釜，加入组分I(为异氰酸酯Ⅰ)99质量份，组分II(为聚醚多元醇①和化合物a1)1质量份，且在组分II中化合物a1的质量含量为32ppm。
S2：打开搅拌，设定搅拌速率为300rad/s，在加热温度为90℃油浴下反应1h，反应完成后降温出料即得聚氨酯胶黏剂。
将所制得的聚氨酯胶黏剂用于无醛添加模压托盘的生产。
制备无醛添加模压托盘：
SS1：原料制备：通过削片、刨片获得杨木原料刨花，干燥后控制刨花含水率在12wt％。
SS2：施胶工序：将聚氨酯胶黏剂以10％的施胶量(以刨花质量计)通过雾化施胶的方式施加在刨花原料上。
SS3：热压工序：在热压机的上下模具各个部分喷涂脱模剂1，待脱模剂无挥发份并在上下模具上成膜后，将施加过聚氨酯胶黏剂的刨花放置于模具中，铺平后在174℃进行热压，保压时间为150s，保压压力为18Mpa。
SS4：后处理工序：将热压出模的模压托盘从热压机中取出后，将边部打磨后，冷却陈放。
实施例2：
制备聚氨酯胶黏剂：
S1：在装有搅拌器、温度计的5L反应釜，加入组分I(为异氰酸酯Ⅱ)80质量份，组分II(为聚醚多元醇②和化合物a2)20质量份，且在组分II中化合物a2的质量含量为100ppm。
S2：打开搅拌，设定搅拌速率为400rad/s，在加热温度为60℃油浴下反应2.5h，反应完成后降温出料即得聚氨酯胶黏剂。
将所制得的聚氨酯胶黏剂用于无醛添加模压托盘的生产。
制备无醛添加模压托盘：
SS1：原料制备：通过削片、刨片获得松木原料刨花，干燥后控制刨花含水率在20wt％。
SS2：施胶工序：将聚氨酯胶黏剂以7％的施胶量(以刨花质量计)通过淋胶的方式施加在刨花原料上。
SS3：热压工序：在热压机的上下模具各个部分喷涂脱模剂2，待脱模剂无挥发份并在上下模具上成膜后，将施加过聚氨酯胶黏剂的刨花放置于模具中，铺平后在200℃进行热压，保压时间为140s，保压压力为14Mpa。
SS4：后处理工序：将热压出模的模压托盘从热压机中取出后，将边部打磨后，冷却陈放。
实施例3：
制备聚氨酯胶黏剂：
S1：在装有搅拌器、温度计的5L反应釜，加入组分I(为异氰酸酯Ⅱ)85质量份，组分II(为聚醚多元醇③和化合物a4)15质量份，且在组分II中化合物a4的质量含量为1％。
S2：打开搅拌，设定搅拌速率为300rad/s，在加热温度为79℃油浴下反应1h，反应完成后降温出料即得聚氨酯胶黏剂。
将所制得的聚氨酯胶黏剂用于无醛添加模压托盘的生产。
制备无醛添加模压托盘：
SS1：原料制备：通过削片、刨片获得竹原料刨花，干燥后控制刨花含水率在10wt％。
SS2：施胶工序：将聚氨酯胶黏剂以4％的施胶量(以刨花质量计)通过雾化施胶的方式施加在刨花原料上。
SS3：热压工序：在热压机的上下模具各个部分喷涂脱模剂1，待脱模剂无挥发份并在上下模具上成膜后，将施加过聚氨酯胶黏剂的刨花放置于模具中，铺平后在143℃进行热压，保压时间为100s，保压压力为16Mpa。
SS4：后处理工序：将热压出模的模压托盘从热压机中取出后，将边部打磨后，冷却陈放。
实施例4：
制备聚氨酯胶黏剂：
S1：在装有搅拌器、温度计的5L反应釜，加入组分I(为异氰酸酯Ⅰ)91质量份，组分II(为聚醚多元醇③和化合物a5)9质量份，且在组分II中化合物a5的质量含量为420ppm。
S2：打开搅拌，设定搅拌速率为500rad/s，在加热温度为71℃油浴下反应1.5h，反应完成后降温出料即得聚氨酯胶黏剂。
将所制得的聚氨酯胶黏剂用于无醛添加模压托盘的生产。
制备无醛添加模压托盘：
SS1：原料制备：通过削片、刨片获得花生壳原料刨花，干燥后控制刨花含水率在15wt％。
SS2：施胶工序：将聚氨酯胶黏剂以5％的施胶量(以刨花质量计)通过淋胶的方式施加在刨花原料上。
SS3：热压工序：在热压机的上下模具各个部分喷涂脱模剂1，待脱模剂无挥发份并在上下模具上成膜后，将施加过聚氨酯胶黏剂的刨花放置于模具中，铺平后在196℃进行热压，保压时间为90s，保压压力为13Mpa。
SS4：后处理工序：将热压出模的模压托盘从热压机中取出后，将边部打磨后，冷却陈放。
实施例5：
制备聚氨酯胶黏剂：
S1：在装有搅拌器、温度计的5L反应釜，加入组分I(为异氰酸酯Ⅱ)95质量份，组分II(为聚醚多元醇①和化合物a6)5质量份，且在组分II中化合物a6的质量含量为1ppm。
S2：打开搅拌，设定搅拌速率为450rad/s，在加热温度为78℃油浴下反应2h，反应完成后降温出料即得聚氨酯胶黏剂。
将所制得的聚氨酯胶黏剂用于无醛添加模压托盘的生产。
制备无醛添加模压托盘：
SS1：原料制备：通过削片、刨片获得杨木原料刨花，干燥后控制刨花含水率在8wt％。
SS2：施胶工序：将聚氨酯胶黏剂以3％的施胶量(以刨花质量计)通过雾化施胶的方式施加在刨花原料上。
SS3：热压工序：在热压机的上下模具各个部分喷涂脱模剂2，待脱模剂无挥发份并在上下模具上成膜后，将施加过聚氨酯胶黏剂的刨花放置于模具中，铺平后在164℃进行热压，保压时间为80s，保压压力为16Mpa。
SS4：后处理工序：将热压出模的模压托盘从热压机中取出后，将边部打磨后，冷却陈放。
实施例6：
制备聚氨酯胶黏剂：
S1：在装有搅拌器、温度计的5L反应釜，加入组分I(为异氰酸酯Ⅲ)86质量份，组分II(为聚醚多元醇①和化合物a1)14质量份，且在组分II中化合物a1的质量含量为5000ppm。
S2：打开搅拌，设定搅拌速率为350rad/s，在加热温度为90℃油浴下反应1h，反应完成后降温出料即得聚氨酯胶黏剂。
将所制得的聚氨酯胶黏剂用于无醛添加模压托盘的生产。
制备无醛添加模压托盘：
SS1：原料制备：通过削片、刨片获得松木原料刨花，干燥后控制刨花含水率在17wt％。
SS2：施胶工序：将聚氨酯胶黏剂以8％的施胶量(以刨花质量计)通过雾化施胶的方式施加在刨花原料上。
SS3：热压工序：在热压机的上下模具各个部分喷涂脱模剂1，待脱模剂无挥发份并在上下模具上成膜后，将施加过聚氨酯胶黏剂的刨花放置于模具中，铺平后在120℃进行热压，保压时间为160s，保压压力为20Mpa。
SS4：后处理工序：将热压出模的模压托盘从热压机中取出后，将边部打磨后，冷却陈放。
对比例1：
与实施例4的工艺条件基本一致，区别点在于：
在步骤S1中的组分II中不含有化合物a5；
在步骤SS3中保压时间为250s。
对比例2：
与实施例4的工艺条件基本一致，区别点在于：
在步骤S1中不使用聚醚多元醇；
在步骤SS3中保压时间为300s。
对比例3：
与实施例4的工艺条件基本一致，区别点在于：
在步骤S1中不使用异氰酸酯；
在步骤SS3中保压时间为400s。
对比例4：
与实施例4的工艺条件基本一致，区别点在于：
在步骤S1中使用化合物a3代替化合物a5；
在步骤SS3中保压时间为230s。
实施例及对比例的测试结果见表1。
以上性能考察按标准GB/T 41231-2021“竹木刨花模压成型托盘通用技术条件”进行测试。
由以上实施例和对比例，基于异氰酸酯、聚醚多元醇和化合物A相互组合进行反应制备得到的聚氨酯胶粘剂，相比于对比文件1、2能大幅缩短托盘热压成型所需的保压时间，生产效率大幅提高，且能显著提升模压托盘的力学性能。
对比实施例1-6与对比例1-3可见，实施例制备的托盘的内结合强度在1.4Mpa-2.0Mpa，加强筋抗弯性能在450kg-627kg，支撑腿抗压强度在2344kg-3231kg，叉举性能在2987kg-3671kg，板面集中载荷在7945kg-9870kg，以上综合力学性能强度远远优于对比例中的综合力学性能。
而通过对比例4的实验结果可见，采用n值大于5的烯丙基醚，在与实施例4基本相同的工艺条件下，需要更长的保压时间才能实现托盘的模压成型，生产效率大幅降低，而且综合力学性能也明显逊色于实施例。
进一步的，通过实施例3-5的实验结果可见，组分II中含有结构式(II)的化合物A相比于含有结构式(I)的化合物A，能够在更短的保压时间内实现托盘的模压成型，能在兼顾优良的产品力学性能的前提下，进一步显著提升生产效率。
容易理解的，上述实施例仅仅是为清楚地说明所作的举例，并不意味着本发明仅局限于此。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (10)
- 一种聚氨酯胶黏剂，其特征在于，所述聚氨酯胶黏剂采用包括组分I和组分II的反应原料经反应获得；其中，所述组分I包括异氰酸酯；所述组分II包括聚醚多元醇和化合物A；所述聚醚多元醇选自聚氧化乙烯多元醇、聚氧化乙烯-氧化丙烯多元醇中的一种或多种；所述化合物A选自如下结构式(I)和结构式(II)的化合物中的一种或多种：
其中，结构式(I)和结构式(II)中的n独立地为1-5的整数；优选的，所述化合物A选自所述结构式(II)的化合物中的一种或多种。 - 根据权利要求1所述的聚氨酯胶黏剂，其特征在于，基于所述组分II的总质量，所述化合物A的含量为1ppm-1％，优选1-500ppm。
- 根据权利要求2所述的聚氨酯胶黏剂，其特征在于，以所述组分I和所述组分II的用量之和为100质量份计：所述组分I的用量为80-99质量份，优选85-95质量份；所述组分II的用量为1-20质量份，优选3-10质量份。
- 根据权利要求1-3任一项所述的聚氨酯胶黏剂，其特征在于，所述聚醚多元醇选自分子量Mn为1000-5000g/mol且官能度2-4的聚氧化乙烯多元醇、聚氧化乙烯-氧化丙烯多元醇中的一种或多种，优选选自分子量Mn为3000-5000g/mol且官能度2-4的聚氧化乙烯多元醇、聚氧化乙烯-氧 化丙烯多元醇中的一种或多种；和/或，所述异氰酸酯的官能度≥2，优选选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯和异佛尔酮二异氰酸酯、多亚甲基多苯基多异氰酸酯中的一种或多种的组合。
- 权利要求1-4任一项所述的聚氨酯胶黏剂的制备方法，其特征在于，将各反应原料混合反应得到所述聚氨酯胶黏剂；优选的，所述反应在60-90℃优选70-80℃下进行，反应时间优选为1-4h，更优选为1.5-2.5h；反应过程中进行搅拌的搅拌速率优选为300-500rad/s，更优选300-400rad/s。
- 权利要求1-4任一项所述的聚氨酯胶黏剂在模压制品中的应用，优选的，所述模压制品包括模压板材和模压托盘中的一种或多种；优选的，所述模压制品的基材材料包括刨花、板、纤维中的一种或多种，优选包括源于草本植物和木本植物的刨花、板、纤维中的一种或多种；优选的，所述模压制品的基材材料包括来源于农林三剩物的材料。
- 一种无醛添加模压托盘，其特征在于，所述模压托盘中所用的胶黏剂为权利要求1-4任一项所述的聚氨酯胶黏剂；优选的，所述模压托盘的基材材料包括刨花、板、纤维中的一种或多种，优选包括源于草本植物和木本植物的刨花、板、纤维中的一种或多种；优选的，所述模压制品的基材材料包括来源于农林三剩物的材料；优选的，所述模压托盘中，所述聚氨酯胶黏剂的用量为所述基材材料质量的3％-10％。
- 权利要求7所述的无醛添加模压托盘的制备方法，其特征在于，所述制备方法包括如下步骤：1)将所述基材材料的含水率控制在8-20wt％；2)将所述聚氨酯胶黏剂施加于所述基材材料上；3)在热压机的模具上施加脱模剂，然后将步骤2)得到的基材材料置于热压机的模具中，之后进行热压以形成所述模压托盘。
- 根据权利要求8所述的制备方法，其特征在于，步骤3)中，进行所述热压时，热压温度为120℃-200℃，保压压力为13-20Mpa，保压时间为80s-300s。
- 根据权利要求9所述的制备方法，其特征在于，所述保压时间为80s-250s，例如为80s-200s。
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