CN114058311A - Modified isocyanate adhesive and preparation method thereof, aldehyde-free mould pressing tray and preparation method thereof - Google Patents
Modified isocyanate adhesive and preparation method thereof, aldehyde-free mould pressing tray and preparation method thereof Download PDFInfo
- Publication number
- CN114058311A CN114058311A CN202010775349.8A CN202010775349A CN114058311A CN 114058311 A CN114058311 A CN 114058311A CN 202010775349 A CN202010775349 A CN 202010775349A CN 114058311 A CN114058311 A CN 114058311A
- Authority
- CN
- China
- Prior art keywords
- modified isocyanate
- adhesive
- isocyanate
- siloxane
- benzene ring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012948 isocyanate Substances 0.000 title claims abstract description 166
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 165
- 239000000853 adhesive Substances 0.000 title claims abstract description 86
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000003825 pressing Methods 0.000 title claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 79
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002023 wood Substances 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 25
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 25
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims description 54
- 230000008569 process Effects 0.000 claims description 33
- 238000007731 hot pressing Methods 0.000 claims description 32
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 20
- 238000004026 adhesive bonding Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000004814 polyurethane Substances 0.000 claims description 10
- 229920002635 polyurethane Polymers 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 9
- -1 polymethylene Polymers 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 238000004513 sizing Methods 0.000 claims description 7
- 241000219000 Populus Species 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- VNBLTKHUCJLFSB-UHFFFAOYSA-N n-(trimethoxysilylmethyl)aniline Chemical compound CO[Si](OC)(OC)CNC1=CC=CC=C1 VNBLTKHUCJLFSB-UHFFFAOYSA-N 0.000 claims description 5
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 244000166124 Eucalyptus globulus Species 0.000 claims description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 2
- 235000011613 Pinus brutia Nutrition 0.000 claims description 2
- 241000018646 Pinus brutia Species 0.000 claims description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 2
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 claims description 2
- 235000013399 edible fruits Nutrition 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 239000012752 auxiliary agent Substances 0.000 claims 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000003973 paint Substances 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 14
- 238000011056 performance test Methods 0.000 abstract description 7
- 238000010998 test method Methods 0.000 abstract description 3
- 239000003292 glue Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000463 material Substances 0.000 description 15
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000035943 smell Effects 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- 101000972853 Hordeum vulgare Non-specific lipid-transfer protein 3 Proteins 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000007766 curtain coating Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000002085 irritant Substances 0.000 description 2
- 231100000021 irritant Toxicity 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 235000019633 pungent taste Nutrition 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 208000013201 Stress fracture Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012771 household material Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012978 lignocellulosic material Substances 0.000 description 1
- 238000005259 measurement Methods 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
- 230000009965 odorless effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 235000019640 taste Nutrition 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N1/00—Pretreatment of moulding material
- B27N1/02—Mixing the material with binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/302—Water
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/778—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur silicon
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a modified isocyanate adhesive and a preparation method thereof. The isocyanate is modified by siloxane containing benzene rings and polyethylene glycol monomethyl ether, so that a molecular chain has good flexibility, and the molecular chain has excellent hydrophilicity, initial viscosity and demolding performance. Meanwhile, the invention also provides an aldehyde-free molded tray and a preparation method thereof, and the prepared aldehyde-free molded tray has no peculiar smell, stable quality and excellent water resistance by introducing the siloxane modified isocyanate adhesive containing the benzene ring into the wood shavings; and the performance of the fork lift test and the stacking test is excellent through the wet performance test according to GB/T4995 plus 2014 'the performance requirement of the universal flat pallet for intermodal and GB/T4996 plus 2014' the test method of the universal flat pallet for intermodal; can be widely applied to consignment of various articles and simultaneously meets the use requirements of indoor and outdoor.
Description
Technical Field
The invention belongs to the field of molded trays, and relates to a modified isocyanate adhesive and a preparation method thereof, and an aldehyde-free molded tray prepared from the adhesive and a preparation method thereof.
Background
With the development of economy, the transportation of goods is increasing, and the demand for pallets is also increasing. In the past, solid wood is used as a raw material to meet the requirements of the pallet market, but with the gradual reduction of forest resources, the price of the raw material rises, and the requirements of factories for preparing pallets by a process which saves more raw materials are forced to reduce the loss of the raw materials. In addition, in the conventional wooden pallets manufactured by using large-diameter wood as a raw material, the strength and durability of the pallets during storage are greatly affected by the temperature and humidity of the use environment, and thus, a technology of manufacturing high-quality wooden pallets by sufficiently using small-diameter grade wood, wood processing residues, and lignocellulosic materials is increasingly gaining attention.
Most of the existing mould pressing tray moulds are of special-shaped structures, and the number of corners is large, compared with the conventional artificial board manufacturing process, the glue solution has higher requirement on the wrapping property of fine materials, the initial viscosity is poor, the materials at the corners of the mould pressing tray are not sufficiently paved, and the performance defect is easily formed; compared with the glue applying process of spraying in the artificial board, the glue applying mode of curtain coating is easier to cause the phenomenon of uneven glue applying.
At present, most of common pallets on the market are urea-formaldehyde glue moulded pallets, the water resistance of the urea-formaldehyde glue pallets is poor, and the pallets are easy to be damaged after being used outdoors for a long time; and the urea-formaldehyde glue tray is easy to release pungent smell in the using process, and the urea-formaldehyde glue tray is placed in a sealed manner for a long time, especially in a high-temperature and high-humidity environment, so that the harm to a human body is great.
The research on the poplar wood shaving molded plane industrial tray in the plum outline and the like provides the poplar wood shaving molded plane industrial tray which has the characteristics of energy conservation, material reduction, excellent performance and the like, but has the problem that the tray releases irritant gas.
CN 102336292A provides a production process of mould pressing tray, and isocyanate and urea glue mixture or phenolic resin and melamine mixture is applied to plant fiber to prepare the mould pressing tray, the density of the tray is high, the reliability is good, but the glue solution contains formaldehyde, the finished tray is placed for a long time, irritant gas is emitted, and the polar group of the urea glue system is more, and the whole water resistance is general.
The isocyanate adhesive has the advantage of environmental protection, and is currently researched in the application of artificial boards. But because the isocyanate has strong reaction capability, phenomena of steel belt sticking, edge breakage in post processing and the like are easy to occur. In the prior art, in order to solve the problem of steel belt sticking, a method of spraying a release agent is generally adopted; in order to solve the problem of edge breakage in post-processing, a method of using a compound urea adhesive together is generally adopted, the process is complicated, the cost is high, and in addition, the isocyanate adhesive has the defects of poor initial viscosity and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a modified isocyanate adhesive and a preparation method thereof, wherein the modified isocyanate adhesive is an aldehyde-free environment-friendly adhesive, a molecular chain has good flexibility through modification of siloxane containing a benzene ring and polyethylene glycol monomethyl ether, and the modified isocyanate adhesive has excellent hydrophilicity, initial viscosity and demolding performance, and can meet the requirement on viscosity in the using process even if no tackifier is added. The glue solution is applied to the artificial board, has good compatibility with other materials such as wood materials and the like, is dispersed more uniformly, and can effectively improve the dimensional stability and edge breakage of the board.
Meanwhile, the invention also provides an aldehyde-free molded tray and a preparation method thereof, the aldehyde-free molded tray is prepared by introducing the siloxane modified isocyanate adhesive containing the benzene ring into wood shavings, and the tray has excellent mechanical property and water resistance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a modified isocyanate adhesive comprises 90-97 wt%, preferably 92-95 wt% of siloxane modified isocyanate containing benzene ring based on the total weight of the adhesive.
In the modified isocyanate adhesive of the present invention, preferably, the content of the isocyanate group (-NCO) in the siloxane modified isocyanate containing a benzene ring is 29 to 31 wt%, preferably 29.5 to 30.5 wt%.
In the modified isocyanate adhesive, the siloxane modified isocyanate containing a benzene ring contains hydroxyl (-OH) and isocyanate (-NCO) groups in a molar ratio of 2-5: 100, preferably 3-4: 100.
In the modified isocyanate adhesive, the siloxane modified isocyanate containing benzene rings has the viscosity of 300-1500 cP, preferably 500-1000 cP; because the structure of the siloxane modified isocyanate containing the benzene ring has certain hydrophilicity and the hydroxyl oxygen on the silane coupling agent has strong polarity, the siloxane modified isocyanate can form certain hydrogen bond action with the surface of a material and process water thereof, the initial viscosity of the modified isocyanate is improved, and the requirement on the viscosity in the use process can be met even if no tackifier is added.
In the modified isocyanate adhesive, the siloxane modified isocyanate containing benzene rings is prepared from a silane coupling agent containing benzene rings and polyethylene glycol monomethyl ether modified isocyanate;
preferably, the mass ratio of the raw material isocyanate to the silane coupling agent containing benzene rings to the polyethylene glycol monomethyl ether is 84.0-94.5: 0.5-2.0: 5 to 14, preferably 88.0 to 92.0: 1.0-1.5: 8-12;
preferably, the isocyanate is selected from one or more of aromatic diisocyanate and derivatives thereof, preferably one or more of polymethylene polyphenyl polyisocyanate, more preferably one or more of polymethylene polyphenyl polyisocyanate with viscosity of 130 to 400mPa s (25 ℃), or NCO content of 30 to 32 wt%; further, the isocyanates include, but are not limited to, Wanhua CW20, CW30, PM400, PM700, and the like, preferably CW 20;
preferably, the silane coupling agent containing a benzene ring has a general molecular structural formula of Y-Ph-Si (OR)3wherein-OR is selected from alkoxy, preferablyMethoxy, ethoxy and the like, Y-is one or more selected from hydroxyl, amino, epoxy and the like, preferably amino, Ph represents phenyl; further, the silane coupling agent containing a benzene ring is specifically phenylaminomethyltrimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, or the like, and phenylaminomethyltrimethoxysilane is preferable.
Furthermore, the modified isocyanate adhesive also comprises 3-10 wt%, preferably 5-8 wt% of a tackifier;
preferably, the tackifier is selected from one or more of EVA emulsion, polyurethane emulsion and the like; preferably, the polyurethane emulsion is a waterborne polyurethane adhesive, the viscosity of the waterborne polyurethane adhesive is 100-1000 mPa & s, the solid content is 45-50 wt%, and the polyurethane emulsion comprises, but is not limited to, Wanhua T0245.
The invention also provides a preparation method of the modified isocyanate adhesive, which comprises the following steps:
1) preparation of siloxane-modified isocyanate containing benzene ring:
uniformly mixing a catalyst, a silane coupling agent containing a benzene ring and polyethylene glycol monomethyl ether at room temperature (generally 5-35 ℃), adding the mixture into isocyanate under the conditions of nitrogen protection and stirring, and carrying out polymerization reaction for 1.5-2.5 h (for example 2h) at 75-85 ℃ (for example 80 ℃) to prepare the siloxane modified isocyanate containing the benzene ring.
2) Preparing the siloxane modified isocyanate containing benzene rings prepared in the step 1) and an optional tackifier into the modified isocyanate adhesive according to the use requirement.
In the present invention, "optional" means the presence or absence of the latter-mentioned component, that is, the component may be 0.
In the preparation method of the present invention, the catalyst in step 1) is selected from at least one of dibutyltin dilaurate, stannous octoate, dibutyltin bis (dodecylthio) and dibutyltin diacetate, preferably dibutyltin dilaurate;
preferably, the catalyst is used in an amount of 0.02 to 0.05 wt%, preferably such as 0.03 wt%, based on the weight of the isocyanate;
preferably, the mixed solution of the catalyst, the silane coupling agent containing the benzene ring and the polyethylene glycol monomethyl ether is slowly added into the isocyanate, and the adding time is 10-40 min, preferably 20-30 min; the dropwise addition is preferred.
In the preparation method of the invention, in the step 2), the siloxane modified isocyanate containing benzene ring and the optional tackifier can be directly mixed to prepare the adhesive for use; the siloxane modified isocyanate containing benzene rings and the tackifier components can also be added respectively according to the process requirements in the preparation process of the plate, and can be specifically selected according to the actual use requirements.
The third aspect of the invention aims to provide the application of the adhesive in the field of artificial boards, and the adhesive can be used for preparing aldehyde-free plywood, flakeboard and molded boards, and is particularly suitable for preparing aldehyde-free molded trays.
An aldehyde-free molded tray comprising 75 to 90 wt%, preferably 80 to 85 wt% of wood shavings, based on 100% by weight of the total weight; and 3 to 10 wt%, preferably 5 to 8 wt%, of the modified isocyanate adhesive;
the aldehyde-free molded tray also preferably contains 5-15 wt%, preferably 8-12 wt% of water.
The aldehyde-free mould pressing tray is characterized in that the wood shavings are selected from one or more of poplar wood shavings, oak wood shavings, pine wood shavings, fruit wood shavings, eucalyptus wood shavings, crop straws and the like, and the poplar wood shavings are preferably selected;
preferably, the strands have a water content of <5 wt%, preferably the strands are oven dried to absolute dryness;
preferably, the width of the wood shavings is 2-7 mm, preferably 4-6 mm; the length is 5-30 mm, preferably 5-30 mm; the thickness is 0.5 to 2mm, preferably 0.8 to 1.5 mm.
The aldehyde-free mould pressing tray is preferably in a four-way fork type, a double-layer Chinese character 'chuan' type, a two-way fork type and the like.
The formaldehyde-free mould pressing tray has the density of 0.9-1.05 g/cm3Preferably 0.95 to 1.0g/cm3。
In another aspect of the present invention, there is provided a method for preparing the above aldehyde-free molded tray, comprising the steps of:
the siloxane modified isocyanate containing benzene ring and optional tackifier are directly mixed to prepare the adhesive for use: directly mixing siloxane modified isocyanate containing benzene rings with an optional tackifier to prepare an adhesive, and uniformly gluing the adhesive on the surface of the wood shavings under the stirring condition; then uniformly applying water to the surface of the wood shavings, paving and hot-press forming;
or
Siloxane modified isocyanate containing benzene rings and a tackifier are respectively added in the preparation process of the plate according to the process requirements: uniformly gluing siloxane modified isocyanate containing benzene rings on the surface of wood shavings under the stirring condition; then mixing the tackifier with water, uniformly gluing the mixture on the surface of the wood shavings, paving and hot-press molding;
in the preparation method of the aldehyde-free mould pressing tray, the glue applying method preferably applies glue to the surface of the wood shavings by curtain coating, and the total glue applying time is 30-180 s, preferably 90-120 s; wherein the sizing time of the siloxane modified isocyanate containing benzene rings is 30-120 s, preferably 60-90 s; the optional tackifier (mixed with water) is applied for 30-60 s, preferably 40-50 s;
in the preparation method of the aldehyde-free mould pressing tray, the hot pressing temperature is 160-180 ℃, and preferably 165-175 ℃; the hot pressing time is 300-400 s, preferably 320-380 s; the hot pressing pressure is 8-10 MPaG, preferably 8.5-9.5 MPaG.
Compared with the prior art, the invention has the following advantages:
(1) the modified isocyanate adhesive is prepared by modifying isocyanate with a silane coupling agent containing a benzene ring and polyethylene glycol monomethyl ether, wherein the silane coupling agent is bonded to an isocyanate molecular chain through the reaction of an active functional group on the benzene ring and-NCO, and the dispersion stability of the silane coupling agent is further improved because the benzene ring is compatible with the isocyanate; the polyethylene glycol monomethyl ether is reacted with-NCO through-OH on a polyether chain, so that the polarity and the flexibility of a molecular chain are improved, and the mobility of a small molecular chain segment is reduced. The benzene ring in the silane coupling agent and the long-chain polyether have synergistic effect, so that the storage stability of the isocyanate adhesive product and the dispersion uniformity of sizing can be obviously improved, and the problem of precipitation in the storage process of the existing siloxane modified isocyanate is effectively solved, and the hydrophilicity and the initial viscosity of the adhesive are further improved.
(2) In the modified isocyanate adhesive, after isocyanate is modified by adopting the silane coupling agent containing benzene rings, the silicon-containing molecular chain segments are uniformly exposed at the outer ends of the molecular chains of the modified isocyanate, so that the structure improves the mold release property of the isocyanate adhesive and avoids the problem of plate bonding by hot pressing of the conventional isocyanate adhesive. And alkoxy in the silane coupling agent is hydrolyzed to form-OH in the hot pressing process, and the-OH can react with isocyanate, so that the crosslinking density of the mould pressing tray is further improved, and the stability of the board manufacturing performance is improved.
(3) In the modified isocyanate adhesive, the introduced polyethylene glycol monomethyl ether contains hydroxyl functional groups with stronger polarity and polyether long straight flexible chains, and the hydrogen bonding effect of polar hydroxyl and the wrapping property of long-chain molecules improve the dispersion stability of the adhesive solution and the wrapping property of fine materials, and improve the uniformity of the adhesive solution in the dispersion process and the hydrophilicity and initial viscosity of the molecular chains.
(4) The modified isocyanate adhesive is used in the production of aldehyde-free molded trays, can overcome the problems of low local bearing strength of the tray, easy generation of stress fracture and local cracking and the like in the prior art, enhances the strength, bearing performance and bearing strength of the tray body, improves the initial adhesion and has good demolding performance; the preparation method has the advantages of mild reaction conditions, high production efficiency (improved by about 10-20%), easiness in industrial production and the like.
The aldehyde-free mould pressing tray prepared by the invention has no peculiar smell, stable quality and excellent water resistance; and the performance of the fork lift test and the stacking test is excellent through the wet performance test according to GB/T4995 plus 2014 'the performance requirement of the universal flat pallet for intermodal and GB/T4996 plus 2014' the test method of the universal flat pallet for intermodal; can be widely applied to consignment of various articles and simultaneously meets the use requirements of indoor and outdoor.
Detailed Description
In order to further explain the technical scheme of the invention, the invention is explained in detail by the specific embodiment
The main raw material sources of the embodiment and the comparative example of the invention
The others are commonly sold raw materials and are not limited by manufacturers.
Method for testing performance of products of inventive example and comparative example
1. And (3) performance testing: GB/T4995- 'intermodal general flat pallet performance requirement and experiment selection' and GB/T4996- 'intermodal general flat pallet test method' test the pallet to test the fork lifting performance and the angle drop performance.
2.2h absorption thickness: GB/T17657 and 2013, 4.5 determination of water absorption thickness expansion rate, method 2 and 2 test of the water absorption thickness expansion rate of the plate within 2 hours.
3. Formaldehyde emission: GB/T17657-2013 stipulate a test method-4.59 formaldehyde release measurement-a dryer method for testing the formaldehyde content of the board.
4. Initial viscosity: laboratory initial tack test standard-push plate measurement. After the materials are evenly glued, the materials are paved in a 20 x 30cm mould, the density is set to be 0.95g/cm3, and after paving is finished, prepressing is carried out for 10-15s under the condition that the surface pressure is 8 MPa.
5. Hot-pressing plate bonding test: and (4) visually observing the area of the material adhered to the hot pressing plate after hot pressing, and judging the quality of the plate adhering performance. The 1 level is a sticky plate; level 2 is that the area of the bonding plate is less than 5%; grade 3 is greater than 5% of the bonding plate area.
6. Construction performance: the quality is evaluated according to the stability of the glue solution, the preparation of the glue solution, the gluing effect, the repair and other easy operation degrees. Grade 1 is excellent in workability; level 2 is to basically meet the construction requirements; grade 3 is poor in workability.
7. Evaluation of odor: refer to the Q/SFYJJ household material odor detection method and technical requirements. Grade 1 is odorless; grade 2 has slight odor; grade 3 smells, but not irritates; grade 4 has pungent odor, or no pungent taste, but has a strong taste; strong pungent taste of grade 5.
Example 1
Preparing a modified isocyanate adhesive:
the mass ratio of the raw material isocyanate to the phenylaminomethyl triethoxysilane to the polyethylene glycol monomethyl ether is 91.2: 1.3: 7.5, the amount of the catalyst dibutyltin dilaurate is 0.02 wt% of the mass of the isocyanate.
1) In the control modification process, OH: NCO ═ 3: 100
Weighing the raw materials according to the proportion, uniformly mixing dibutyltin dilaurate, phenylaminomethyl triethoxysilane and polyethylene glycol monomethyl ether at room temperature, slowly dripping into CW20 under the conditions of nitrogen protection and stirring, dripping for 30min, and carrying out polymerization reaction for 2h at 80 ℃ to obtain the siloxane modified isocyanate containing benzene rings. The prepared siloxane modified isocyanate containing benzene rings has the NCOwt% content of 30.5% and the viscosity of 500 cP.
2) Preparing the siloxane modified isocyanate containing benzene rings prepared in the step 1) and T0245 into a modified isocyanate adhesive according to the use requirement, wherein the ratio of the modified isocyanate adhesive to the T0245 is 27.5: 1.
Preparing an aldehyde-free molded tray:
according to actual use, siloxane modified isocyanate containing benzene rings and the T0245 component in the modified isocyanate adhesive are respectively added in the preparation process of the mould pressing tray according to the process requirements.
The percentage composition of the materials comprises:
80 wt% of wood shavings
8.5 wt% of modified isocyanate adhesive
11.5 wt% of process water
Preparing 17kg of a tray with the size of 1.14 multiplied by 1.14m and the thickness of 11.5mm, and uniformly gluing the siloxane modified isocyanate containing the benzene ring on the surface of the wood shavings under the stirring condition for 90 s; then mixing the tackifier T0245 and process water, uniformly gluing the mixture on the surface of the wood shaving for 50s, paving the wood shaving in a mould after uniform mixing, and hot-pressing and molding; the hot pressing temperature is 170 ℃, the hot pressing time is 350s, and the hot pressing pressure is 8 MPaG.
The performance of the trays was tested according to the "Performance test methods for the products of the examples according to the invention and comparative examples". See table 1 for details.
Example 2
Preparing a modified isocyanate adhesive:
the mass ratio of the raw material isocyanate to the phenylaminomethyl triethoxysilane to the polyethylene glycol monomethyl ether is 93.4: 1.5: 5.1, the amount of dibutyltin dilaurate used as the catalyst is 0.02 wt% of the mass of the isocyanate.
1) In the control modification process, OH: NCO ═ 2: 100
Weighing the raw materials according to the proportion, and uniformly mixing dibutyltin dilaurate, phenylaminomethyl trimethoxy silane and polyethylene glycol monomethyl ether at room temperature; then slowly dropwise adding the mixture into CW30 under the conditions of nitrogen protection and stirring, wherein the dropwise adding time is 10min, and carrying out polymerization reaction for 1.5h at 75 ℃ to obtain the siloxane modified isocyanate containing benzene rings. The prepared siloxane modified isocyanate containing benzene rings has the NCOwt% content of 30.8% and the viscosity of 380 cP.
2) Preparing the siloxane modified isocyanate containing benzene rings prepared in the step 1) and T0245 into a modified isocyanate adhesive according to the use requirement, wherein the ratio of the modified isocyanate adhesive to the T0245 is 25/12.5: 1
Preparing an aldehyde-free molded tray:
according to actual use, siloxane modified isocyanate containing benzene rings and the T0245 component in the modified isocyanate adhesive are respectively added in the preparation process of the mould pressing tray according to the process requirements.
The percentage composition of the materials comprises
75 wt% of wood shavings
10.4 wt% of modified isocyanate adhesive
14.6 wt% of process water
According to the market application requirements, preparing 17kg of a tray with the size of 1.14 multiplied by 1.14m and the thickness of 12mm, uniformly gluing siloxane modified isocyanate containing benzene rings on the surface of the wood shavings under the stirring condition, wherein the gluing time is 60 s; then, mixing the T0245 and process water, uniformly gluing the mixture on the surface of the wood shaving for 50s, paving the wood shaving in a mould after uniform mixing, and hot-pressing and molding; the hot pressing temperature is 165 ℃, the hot pressing time is 360s, and the hot pressing pressure is 9 MPaG.
The performance of the trays was tested according to the "Performance test methods for the products of the examples according to the invention and comparative examples". See table 1 for details.
Example 3
Preparing a modified isocyanate adhesive:
the mass ratio of the raw material isocyanate to the phenylaminomethyl triethoxysilane to the polyethylene glycol monomethyl ether is 87.5: 0.5: 12, the using amount of the catalyst stannous octoate is 0.03 weight percent of the mass of the isocyanate.
1) In the control modification process, OH: NCO ═ 5:100
Weighing the raw materials according to the proportion, and uniformly mixing stannous octoate, phenylaminomethyl triethoxysilane and polyethylene glycol monomethyl ether at room temperature; then slowly dropwise adding the mixture into PM400 under the conditions of nitrogen protection and stirring, wherein the dropwise adding time is 20min, and carrying out polymerization reaction for 1.5h at 75 ℃ to obtain the siloxane modified isocyanate containing benzene rings. The prepared siloxane modified isocyanate containing benzene rings has the NCOwt% content of 29.8% and the viscosity of 1200 cP.
2) Preparing the siloxane modified isocyanate containing benzene rings prepared in the step 1) and T0245 into a modified isocyanate adhesive according to the use requirement, wherein the ratio of the modified isocyanate adhesive to the T0245 is 10: 1
Preparing an aldehyde-free molded tray:
according to actual use, siloxane modified isocyanate containing benzene rings and the T0245 component in the modified isocyanate adhesive are respectively added in the preparation process of the mould pressing tray according to the process requirements.
The percentage composition of the materials comprises
90 wt% of wood shavings
3.3 wt% of modified isocyanate adhesive
7 wt% of process water
According to the market application requirements, preparing 17kg of a tray with the size of 1.14 multiplied by 1.14m and the thickness of 12.3mm, uniformly gluing siloxane modified isocyanate containing benzene rings on the surface of the wood shavings under the stirring condition, wherein the gluing time is 70 s; then mixing the tackifier T0245 and process water, uniformly gluing the mixture on the surface of the wood shaving for 45s, paving the wood shaving in a mould after uniform mixing, and hot-pressing and molding; the hot pressing temperature was 175 deg.C, the hot pressing time was 320s, and the hot pressing pressure was 9.5 MPaG.
The performance of the trays was tested according to the "Performance test methods for the products of the examples according to the invention and comparative examples". See table 1 for details.
Example 4
Preparing a modified isocyanate adhesive:
the mass ratio of the raw material isocyanate to the phenylaminomethyl triethoxysilane to the polyethylene glycol monomethyl ether is 88.7:1.5:9.7, and the dosage of the catalyst dibutyltin diacetate is 0.4 wt% of the mass of the isocyanate.
1) In the control modification process, OH: NCO ═ 4:100
Weighing the raw materials according to the proportion, and uniformly mixing dibutyltin diacetate, phenylaminomethyl triethoxysilane and polyethylene glycol monomethyl ether at room temperature; then slowly dropwise adding the mixture into PM700 under the conditions of nitrogen protection and stirring, wherein the dropwise adding time is 40min, and carrying out polymerization reaction for 1.5h at 75 ℃ to obtain the siloxane modified isocyanate containing benzene rings. The prepared siloxane modified isocyanate containing benzene rings has the NCOwt% content of 30.2% and the viscosity of 800 cP.
2) Preparing the siloxane modified isocyanate containing benzene rings prepared in the step 1) and T0245 into a modified isocyanate adhesive according to the use requirement, wherein the ratio of the modified isocyanate adhesive to the T0245 is 18:1
Preparing an aldehyde-free molded tray:
the percentage composition of the materials comprises
85 wt% of wood shavings
6.0 wt% of modified isocyanate adhesive
9 wt% of process water
According to the market application requirements, preparing 17kg of a tray with the size of 1.14 multiplied by 1.14m and the thickness of 12mm, uniformly gluing siloxane modified isocyanate containing benzene rings on the surface of the wood shavings under the stirring condition, wherein the gluing time is 80 s; then mixing the tackifier T0245 and process water, uniformly gluing the mixture on the surface of the wood shaving for 50s, paving the wood shaving in a mould after uniform mixing, and hot-pressing and molding; the hot pressing temperature was 165 ℃, the hot pressing time was 330s, and the hot pressing pressure was 10 MPaG.
The performance of the trays was tested according to the "Performance test methods for the products of the examples according to the invention and comparative examples". See table 1 for details.
Example 5
Preparing a modified isocyanate adhesive:
1) according to the modification scheme of the modified isocyanate adhesive in example 4, the prepared siloxane modified isocyanate containing the benzene ring has the NCOwt% content of 30.2% and the viscosity of 800cP
2) Directly using siloxane modified isocyanate containing benzene ring prepared in the step 1) with 100% content as modified isocyanate adhesive without adding tackifier.
Preparing an aldehyde-free molded tray:
the percentage composition of the materials comprises:
85 wt% of wood shavings
7 wt% of modified isocyanate adhesive
8 wt% of process water
Preparing 17kg of a tray with the size of 1.14 multiplied by 1.14m and the thickness of 11.3mm, and uniformly gluing the modified isocyanate adhesive on the surface of the wood shavings under the stirring condition for 70 s; then evenly applying the process water to the surface of the wood shavings for 20s, paving the wood shavings in a mould after evenly mixing, and carrying out hot press molding; the hot pressing temperature is 165 ℃, the hot pressing time is 300s, and the hot pressing pressure is 10 MPaG.
The performance of the trays was tested according to the "Performance test methods for the products of the examples according to the invention and comparative examples". See table 1 for details.
Comparative example 1
The silane coupling agent containing a benzene ring (phenylaminomethyltriethoxysilane) in example 4 was replaced with 3-triethoxysilyl-1-propylamine, and the conditions were unchanged to give a siloxane-modified isocyanate having a NCOwt% content of 30.2% and a viscosity of 800 cP.
Molded trays were prepared using the above-described modified isocyanates according to example 4 and tested for their performance. See table 1 for details.
Comparative example 2
In the method for modifying isocyanate in example 3, only phenylaminomethyl triethoxysilane is used to modify isocyanate, polyethylene glycol monomethyl ether is not added, other conditions are not changed, and siloxane modified isocyanate containing benzene ring is prepared, wherein the NCOwt% content is 31.4%, and the viscosity is 230 cP.
Molded trays were prepared and tested for performance using the modified isocyanates described above in accordance with example 3. See table 1 for details.
Comparative example 3
In the method for modifying isocyanate in example 1, the silane coupling agent containing benzene ring is replaced by 3-triethoxysilyl-1-propylamine modified isocyanate, polyethylene glycol monomethyl ether is not added, other conditions are not changed, and the prepared siloxane modified isocyanate has the NCOwt% content of 31.4% and the viscosity of 230 cP.
Molded trays were prepared and tested for performance as in example 1 using the modified isocyanate described above. See table 1 for details.
Comparative example 4
In the method for modifying isocyanate in example 4, only polyethylene glycol monomethyl ether is used to modify isocyanate, no silane coupling agent containing benzene ring is added, and other conditions are unchanged, so that the prepared siloxane modified isocyanate containing benzene ring has the NCOwt% content of 30.5% and the viscosity of 770 cP.
Molded trays were prepared using the above-described modified isocyanates according to example 4 and tested for their performance. See table 1 for details.
Comparative example 5
Uniformly mixing dibutyltin dilaurate, phenylaminomethyl triethoxysilane and polyethylene glycol monomethyl ether at room temperature according to the proportion of 1:3.7: 24.3; and slowly dripping 52.57g of the mixed solution into 400g of CW30 for 10min, and stirring at room temperature for 30min to obtain the isocyanate glue solution after physical blending.
Using the above isocyanate glue solution, an aldehyde-free molded tray was prepared according to the method of example 5, and the performance of the tray was tested. See table 1 for details.
Comparative example 6
The adhesive comprises the following components in percentage by weight
82% by weight of wood shavings
15 wt% of urea glue
3% by weight of isocyanate
Molded trays were prepared using the above adhesive according to example 5 and tested for performance. See table 1 for details.
Comparative example 7
The adhesive comprises the following components in percentage by weight
80 wt% of wood shavings
20 wt% of urea glue
Molded trays were prepared using the above adhesive according to example 5 and tested for performance. See table 1 for details.
Table 1 results of performance testing
From the above data it can be seen that: comparative example 1 the storage stability of the glue solution was slightly poor due to the use of a coupling agent containing no benzene ring silane; comparative example 2/3, because no polyether modification was added, the modified isocyanate had poor hydrophilicity, resulting in poor sizing uniformity and workability grade 3; comparative example 4, hot-press plate adhesion resulted from no addition of silane coupling agent; compared with the prior art, the modified isocyanate is in-situ physical blending, the glue preparation is complex, and the construction performance is 3-grade; comparative example 6/7, the panel produced had an irritating odor release during storage due to the addition of the urea glue.
The method can prepare the aldehyde-free molded tray, has certain demolding performance, is matched with the existing molded tray equipment/process, has excellent tray performance, greatly improves the storage stability of the modified isocyanate by modifying the isocyanate with the benzene ring silane coupling agent, has no precipitation in the storage process, and has good construction performance and good hot-pressing plate adhesion.
Claims (10)
1. A modified isocyanate adhesive comprising from 90 to 97 wt%, preferably from 92 to 95 wt%, based on the total weight of the adhesive, of a siloxane modified isocyanate containing benzene rings;
preferably, the content of the isocyanate group in the siloxane modified isocyanate containing the benzene ring is 29 to 31 wt%, preferably 29.5 to 30.5 wt%.
2. The modified isocyanate adhesive according to claim 1, wherein the siloxane modified isocyanate containing a benzene ring contains hydroxyl groups and isocyanate groups in a molar ratio of 2-5: 100, preferably 3-4: 100;
the siloxane modified isocyanate containing the benzene ring has the viscosity of 300-1500 cP, and preferably 500-1000 Cp.
3. The modified isocyanate adhesive according to claim 1 or 2, wherein the siloxane-modified isocyanate containing a benzene ring is prepared from a silane coupling agent containing a benzene ring and polyethylene glycol monomethyl ether-modified isocyanate;
preferably, the mass ratio of the raw material isocyanate to the silane coupling agent containing benzene rings to the polyethylene glycol monomethyl ether is 84.0-94.5: 0.5-2.0: 5 to 14, preferably 88.0 to 92.0: 1.0-1.5: 8-12;
preferably, the isocyanate is selected from one or more of aromatic diisocyanate and derivatives thereof, preferably one or more of polymethylene polyphenyl polyisocyanate, more preferably one or more of polymethylene polyphenyl polyisocyanate with viscosity of 130 to 400mPa s (25 ℃), or NCO content of 30 to 32 wt%;
preferably, the molecular structure of the silane coupling agent containing benzene ringHas the formula of Y-Ph-Si (OR)3wherein-OR is selected from alkoxy, preferably methoxy OR ethoxy, Y-is selected from one OR more of hydroxy, amino and epoxy, preferably amino, Ph represents phenyl; further, the silane coupling agent containing a benzene ring is phenylaminomethyltrimethoxysilane, methylphenyldimethoxysilane or diphenyldimethoxysilane, and preferably phenylaminomethyltrimethoxysilane.
4. The modified isocyanate adhesive according to any one of claims 1 to 3, further comprising 3 to 10 wt%, preferably 5 to 8 wt% of a tackifier;
preferably, the tackifier is selected from one or more of EVA emulsion and polyurethane emulsion; more preferably, the polyurethane emulsion is a waterborne polyurethane adhesive, the viscosity of the waterborne polyurethane adhesive is 100-1000 mPa & s, the solid content is 45-50 wt%, and the polyurethane emulsion comprises, but is not limited to, Wanhua T0245.
5. A method of preparing the modified isocyanate adhesive of any one of claims 1 to 4, comprising the steps of:
1) preparation of siloxane-modified isocyanate containing benzene ring:
uniformly mixing a catalyst, a silane coupling agent containing a benzene ring and polyethylene glycol monomethyl ether, adding the mixture into isocyanate under the conditions of nitrogen protection and stirring, and carrying out polymerization reaction at 75-85 ℃ for 1.5-2.5 h to prepare siloxane modified isocyanate containing a benzene ring;
2) preparing the siloxane modified isocyanate containing the benzene ring prepared in the step 1) and an optional tackifier into a modified isocyanate adhesive.
6. The production method according to claim 5, wherein the catalyst in step 1) is at least one selected from the group consisting of dibutyltin dilaurate, stannous octoate, dibutyltin bis (dodecylthio) and dibutyltin diacetate, preferably dibutyltin dilaurate;
preferably, the amount of the catalyst is 0.02-0.05 wt% of the weight of the isocyanate;
preferably, the mixed solution of the catalyst, the silane coupling agent containing the benzene ring and the polyethylene glycol monomethyl ether is added into isocyanate, and the adding time is 10-40 min, preferably 20-30 min; in the step 2), siloxane modified isocyanate containing benzene rings and an auxiliary agent can be directly mixed to prepare an adhesive; or the siloxane modified isocyanate containing benzene rings and the auxiliary agent can be added respectively in the process of preparing the plate.
7. Use of the modified isocyanate adhesive according to any one of claims 1 to 4 or the modified isocyanate adhesive prepared by the method according to claims 5 to 6 in the field of artificial boards.
8. An aldehyde-free molded tray, characterized by comprising 75 to 90 wt%, preferably 80 to 85 wt% of wood shavings, based on 100 wt% of the total weight; and 3 to 10 wt.%, preferably 5 to 8 wt.%, of the modified isocyanate adhesive of any one of claims 1 to 4 or the modified isocyanate adhesive prepared by the process of claims 5 to 6;
preferably, the water-soluble paint also comprises 5-15 wt%, preferably 8-12 wt% of water.
9. The aldehyde-free molded tray according to claim 8, wherein the wood shavings are selected from one or more of poplar shavings, oak shavings, pine shavings, fruit tree shavings, eucalyptus shavings, and crop stalks, preferably poplar shavings;
the aldehyde-free mould pressing tray is in a four-way fork type, a double-layer III-shaped type or a two-way fork type;
the density of the aldehyde-free mould pressing tray is 0.9-1.05 g/cm3Preferably 0.95 to 1.0g/cm3。
10. A method for preparing the aldehyde-free molded tray according to claim 8 or 9, comprising the steps of:
directly mixing siloxane modified isocyanate containing benzene rings with an optional tackifier to prepare an adhesive, and uniformly gluing the adhesive on the surface of the wood shavings under the stirring condition; then uniformly applying water to the surface of the wood shavings, paving and hot-press forming;
or
Uniformly gluing siloxane modified isocyanate containing benzene rings on the surface of wood shavings under the stirring condition; then mixing the optional tackifier with water, uniformly gluing the mixture on the surface of the wood shaving, paving and hot-press molding;
the sizing method preferably comprises the steps of spraying and sizing on the surface of the wood shaving, wherein the total sizing time is 30-180 s, and preferably 90-120 s; wherein the sizing time of the siloxane modified isocyanate containing benzene rings is 30-120 s, preferably 60-90 s; the optional auxiliary agent is applied for 30-60 s, preferably 40-50 s;
hot pressing is carried out, wherein the hot pressing temperature is 160-180 ℃, and is preferably 165-175 ℃; the hot pressing time is 300-400 s, preferably 320-380 s; the hot pressing pressure is 8-10 MPaG, preferably 8.5-9.5 MPaG.
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| WO2024124372A1 (en) * | 2022-12-12 | 2024-06-20 | 万华化学集团股份有限公司 | Polyurethane adhesive, formaldehyde-additive-free presswood pallet, and preparation method therefor |
| CN118456589A (en) * | 2024-05-09 | 2024-08-09 | 广西扶绥润泓木业有限公司 | Low-density formaldehyde-free shaving board and preparation process thereof |
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