CN116285216A - Production method of amino molding powder - Google Patents
Production method of amino molding powder Download PDFInfo
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- CN116285216A CN116285216A CN202211688045.3A CN202211688045A CN116285216A CN 116285216 A CN116285216 A CN 116285216A CN 202211688045 A CN202211688045 A CN 202211688045A CN 116285216 A CN116285216 A CN 116285216A
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- formaldehyde
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- 238000000465 moulding Methods 0.000 title claims abstract description 33
- 239000000843 powder Substances 0.000 title claims abstract description 30
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 116
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000661 sodium alginate Substances 0.000 claims abstract description 24
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 24
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 24
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 22
- 229920000615 alginic acid Polymers 0.000 claims abstract description 22
- 229940072056 alginate Drugs 0.000 claims abstract description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004202 carbamide Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 18
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007859 condensation product Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 238000006482 condensation reaction Methods 0.000 claims description 10
- 238000004898 kneading Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 claims description 9
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- 239000000737 potassium alginate Substances 0.000 claims description 7
- 235000010408 potassium alginate Nutrition 0.000 claims description 7
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 239000011630 iodine Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 229920001131 Pulp (paper) Polymers 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 claims description 3
- 238000007259 addition reaction Methods 0.000 claims description 3
- 238000000691 measurement method Methods 0.000 claims 1
- 229920001807 Urea-formaldehyde Polymers 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 8
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 abstract description 7
- 239000000178 monomer Substances 0.000 abstract description 7
- 125000003172 aldehyde group Chemical group 0.000 abstract description 6
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 239000000945 filler Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000006068 polycondensation reaction Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008098 formaldehyde solution Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- 241000219000 Populus Species 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000407 epitaxy Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 241001474374 Blennius Species 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- -1 aldehyde amine Chemical class 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000199919 Phaeophyceae Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 235000015243 ice cream Nutrition 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08L61/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention relates to the technical field of amino molding, in particular to a production method of amino molding powder, which takes urea and formaldehyde resin as base materials, alpha-cellulose as filler and oxidized sodium alginate as auxiliary materials, uronic acid monomers of sodium alginate molecules have a cis-diol structure, wherein C-C bonds are oxidized by a strong oxidant to generate two aldehyde groups, and partial formaldehyde is replaced by the aldehyde groups, so that the resin strength is improved, the formaldehyde release amount is reduced, the reaction between oxidized alginate and urea formaldehyde reaction substances occurs, the strength is higher than that of pure urea formaldehyde resin, meanwhile, the free formaldehyde can be reduced to 0.12 percent from 0.42 percent due to the reaction between oxidized sodium alginate and urea formaldehyde substances, and further the formaldehyde release rate is reduced. The product has good mechanical property, impact resistance, uneasy breakage, high hardness, good finish and permanent antistatic property.
Description
Technical Field
The invention belongs to the technical field of amino molding, and particularly relates to a production method of amino molding powder.
Background
Industrial alginic acid can be extracted from various brown algae plants, and the seaweed has large algae body, high yield, abundant resources and easy collection as industrial raw materials. Since 1884, urea-formaldehyde resin is synthesized for the first time, the method has the advantages of high reactivity, short curing time, low cost and the like. However, UF resins release formaldehyde and are harmful to humans indoors. Chinese patent CN201610526435.9 of 10 month 12 in 2016 discloses an antibacterial amino molding compound which is prepared by adding bamboo pulp to match with juice of fresh radix Rumicis Japonici, and changing filler, so that the material has very good antibacterial performance, and melamine is used. In order to improve the performance of UF and inhibit the release of formaldehyde, the UF resin is made into an environment-friendly material, and structural change and the relation between the structural change and the synthesis process condition in the UF forming process are improved, so that the UF resin is a feasible method for effectively controlling the structure and the performance of the UF resin. The melamine has the same function as urea, so that the melamine is the most commonly used modifying reagent in UF composite modification, can react with water-absorbing groups in UF, is alkaline, can neutralize excessive acid in UF, has a stable cyclic structure, can effectively improve the hydrolysis activation energy of UF, and reduces the hydrolysis and thermal degradation speed of UF to a certain extent. With the enhancement of environmental awareness, people have increasingly strict requirements on the content of organic volatile matters (VOC) harmful to bodies, particularly the content of formaldehyde. Therefore, unreacted free formaldehyde during UF formation and formaldehyde released during use due to aging become hot spot problems of research concern. Those skilled in the art are required to develop a method for producing an amino molding powder to meet the existing use requirements and performance requirements.
Disclosure of Invention
The invention aims at solving the existing problems and provides a production method of amino molding powder.
The production method of the amino molding powder comprises the conventional steps of carrying out a contact addition reaction on formaldehyde and urea in a molar ratio of 1:1-1.5 to generate methylol urea, and specifically comprises the following steps of: pumping formaldehyde solution metered by a formaldehyde metering tank into a polycondensation reaction kettle, adding metered hexamethylenetetramine into the reaction kettle through a feeding hole, starting a stirrer, adjusting the pH to 7.8-8.2 by using sodium hydroxide, heating to 58-62 ℃, and adding urea;
the method also comprises the following steps: (1) Sealing the reaction kettle, keeping the temperature in the reaction kettle at 58-62 ℃, adding oxidized alginate accounting for 15-35wt% of urea, continuously stirring for 5-10 min, and performing condensation reaction to obtain a netty foam-like solid with a bodily form structure, thus obtaining a condensation product; (2) Conveying the condensation product to a resin intermediate tank through a closed pipeline, discharging the condensation product to a kneader through a self-flowing pipeline, adding ammonium chloride, wood pulp and lithium stearate, and kneading for 10-15 min at a kneading temperature of 60-65 ℃; (3) drying; (4) crushing; (5) ball milling; (6) sieving and packaging.
Sodium alginate is the seaweed chemical product with the largest sales volume in the world at present. The uronic acid monomer of the sodium alginate molecule has a cis-diol structure, wherein the C-C bond is oxidized by a strong oxidant to generate two aldehyde groups.
Further, the alginate is one of sodium alginate and potassium alginate, the oxidation degree of the oxidized alginate is 15-35% according to the iodine amount measuring method, M w 2 to 15 tens of thousands, and the polydispersity is 1.6 to 2.
Further, the condition of the condensation reaction is that the pH value is 6.5-6.8, the temperature is 65-75 ℃, and the constant temperature reaction time is 90-100 min.
Further, the alginate is one of sodium alginate and potassium alginate, the oxidation degree of the oxidized alginate is 15-35% according to the iodine amount measuring method, M w 2 to 15 tens of thousands, and the polydispersity is 1.6 to 2.
Further, the drying process is that the temperature is 60-80 ℃ and the drying time is 1-2 hours.
Further, 100 parts of urea, 5-8 parts of hexamethylenetetramine, 0.4-0.6 part of ammonium chloride, 60-70 parts of alpha-cellulose and 0.5-1 part of lithium stearate.
The basic reaction for urea formaldehyde polycondensation is aldehyde amine polycondensation. Firstly, amino groups in urea molecules are added with formaldehyde to generate methylol urea, then, dehydration or addition reaction is carried out between hydroxymethyl groups, between hydroxymethyl groups and amino groups, between amino groups and formaldehyde, between oxidized alginate and between imino groups and formaldehyde in different molecules in a system to carry out polycondensation, and finally, the polymer with a bodily structure, namely urea formaldehyde resin, is formed.
The oxidized alginate undergoes the following chemical reaction in the polycondensation system, wherein R is methylene, methylene ether, as shown below:
the invention has the beneficial effects that:
alginate, such as sodium alginate, has been used primarily in the past as a food additive for use as a foaming agent and stabilizer for ice cream and as a thickener for jam cans. In the daily amino molding powder production practice, the inventor tries to improve the processing performance of the prior A1 and A5 urea resin amino molding powder by adding a small amount of dispersing agent and thickening agent in a conventional thinking manner, so that the production and processing process is more stable, the product quality is more balanced, and quite different results are unexpectedly obtained. When the derivative of alginate, oxidized alginate, is used, it has been unexpectedly found that the properties of urea-formaldehyde resin amino molding powder are significantly altered, unlike conventional urea-formaldehyde resin amino molding powder, by not adding small amounts of dispersant and thickener. Through long-time production experiments and experience summarization, the invention discloses a production method of amino molding powder, wherein oxidized alginate is adopted to participate in a synthesis reaction in the synthesis process of urea-formaldehyde resin amino molding powder, uronic acid monomers of sodium alginate molecules have a cis-diol structure, C-C bonds in the uronic acid monomers are oxidized by a strong oxidant to generate two aldehyde groups, and partial formaldehyde is replaced by the uronic acid monomers, so that the strength of resin is improved, the release amount of formaldehyde is reduced, and the obtained oxidized sodium alginate has crosslinking performance and can play a role in crosslinking. To a certain extent, the strength of the amino molding powder improves with the increase of the use amount of oxidized alginate. Compared with pure urea formaldehyde resin, the oxidized alginate and urea formaldehyde reaction substance have more branched structures, the strength is higher than that of the pure urea formaldehyde resin, and meanwhile, the free formaldehyde can be reduced from 0.42% to 0.12% due to the reaction between the oxidized alginate sodium and urea formaldehyde substance, so that more free formaldehyde is consumed in the modified urea formaldehyde resin, and the formaldehyde release rate is further reduced.
Compared with the prior art, the invention has the following advantages:
the invention discloses a production method of base molding powder, which uses urea and formaldehyde resin as base materials, alpha-cellulose as filler and oxidized alginate as auxiliary materials, wherein uronic acid monomers of alginate molecules have a cis-diol structure, and C-C bonds in the uronic acid monomers are oxidized by a strong oxidant to generate two aldehyde groups, and partial formaldehyde is replaced by the aldehyde groups, so that the formaldehyde release amount is reduced, and the reaction between oxidized alginate and UF substances occurs. In addition, the urea resin has more branched structures than pure urea resin, and is suitable for hot press molding under the condition of heating and pressurizing. The molded plastic part is odorless, has good physical and mechanical properties and electrical insulation properties, and has good mechanical properties, impact resistance, low brittleness, high hardness, good smoothness and permanent antistatic property. In addition, after the plywood is prepared by cementing amino molding powder, the formaldehyde emission and the climatic box method measurement value are measured by a perforation extraction method, and the formaldehyde emission E of the board can be achieved 0 Stage requirements.
Detailed Description
The invention is illustrated, but not limited, by the following specific examples.
Example 1
Preparing materials: the molar ratio of formaldehyde to urea is 1:1.5, and the specific production process comprises the following steps of: (1) Pumping 37% formaldehyde solution metered by a formaldehyde metering tank into a Zheng Tang K-1000L polycondensation reaction kettle, adding metered hexamethylenetetramine into the reaction kettle through a feeding hole, starting a stirrer, adjusting the pH to 8.2 by potassium hydroxide, heating to 58 ℃, and adding urea; (3) Sealing the reaction kettle, keeping the temperature in the reaction kettle at 58 ℃, adding oxidized potassium alginate, continuously stirring for 10min, and performing condensation reaction to obtain a netty foam-like solid product, wherein the pH value of the condensation reaction is 6.8, the temperature is 75 ℃, and the constant-temperature reaction time is 100min; (3) Conveying the condensation product to a resin intermediate tank through a closed pipeline, discharging the condensation product to a Honno NH-2000L kneader through a pipeline, adding ammonium chloride, wood pulp and lithium stearate, kneading for 15min, and controlling the kneading temperature to 65 ℃; (4) drying at 70 ℃ for 1.5h; (6) crushing: crushing the tin epitaxy WH-400 crusher at the rotating speed of 3400 rpm; (6) ball milling; (7) sieving, sieving the powder with a 325-mesh sieve, and packaging.
Wherein, 6 parts of potassium alginate of the open moon electrode grade is dispersed in 60 parts of deionized water in a reaction kettle under the condition of light shielding at room temperature, aqueous solution of sodium periodate is added under the stirring condition of 300rpm, deionized water is continuously added until 100 parts of water are contained, after reaction for 6 hours, 0.3 part of salt and 50 parts of alcohol are added for precipitation and suction filtration, and then deionized water is used for dissolution, alcohol precipitation and suction filtration, and drying for 12 hours at 50 ℃ after suction filtration, thus obtaining white potassium alginate oxide, the oxidation degree of the potassium alginate oxide is 15 percent according to the iodine amount measuring method, M w 2 ten thousand, the polydispersity is 1.6.
Example 2
Preparing materials: the molar ratio of formaldehyde to urea is 1:1.5, and the urea is 100 parts by weight, 8 parts by weight of hexamethylenetetramine, 0.6 part by weight of ammonium chloride, 70 parts by weight of brocade alpha-cellulose, 1 part by weight of lithium stearate and 35 parts by weight of oxidized sodium alginate. The specific production process comprises the following steps: (1) Pumping 37% formaldehyde solution which is measured by a formaldehyde measuring tank into a Zheng Tang K-1000L polycondensation reaction kettle, adding the measured hexamethylenetetramine into the reaction kettle through a feeding hole, starting a stirrer, adjusting the pH value to be 6.8 by sodium hydroxide, heating to 62 ℃, and adding urea; (3) Sealing the reaction kettle, keeping the temperature in the reaction kettle at 62 ℃, adding oxidized sodium alginate, continuously stirring for 10min, performing condensation reaction, wherein the pH value of the condensation reaction is 6.8, the temperature is 75 ℃, and the constant-temperature reaction time is 100min, so that the product becomes a foam solid with a reticular structure, and a condensation product is obtained; (3) Conveying the condensation product to a resin intermediate tank through a closed pipeline, discharging the condensation product to a Honno NH-2000L kneader through a pipeline, adding ammonium chloride, wood pulp and lithium stearate, kneading for 15min, and controlling the kneading temperature to 65 ℃; (4) drying at 80 ℃ for 2 hours; (6) crushing: crushing the tin epitaxy WH-400 crusher at the rotating speed of 3400 rpm; (6) ball milling; (7) sieving, sieving the powder with a 325-mesh sieve, and packaging.
Wherein, the oxidized sodium alginate is prepared by dispersing 6 parts of Mingya LY1 sodium alginate in 60 parts of deionized water in a reaction kettle under the condition of light shielding at room temperature, adding aqueous solution of sodium periodate under the stirring condition of 300rpm, continuously adding deionized water until the aqueous solution is 100 parts, reacting for 8 hours, adding 0.3 part of salt and 50 parts of alcohol, precipitating and filtering, dissolving with deionized water, precipitating and filtering with alcohol, drying at 60 ℃ for 14 hours after filtering to obtain white oxidized sodium alginate, wherein the oxidation degree of the oxidized sodium alginate is 135 percent according to an iodine content measuring method, and M w 15 ten thousand, and the polydispersity is 2.
Comparative example 1
In this comparative example, compared with example 2, oxidized sodium alginate was not added during the production, and the rest of the procedure was the same as in example 2.
100 parts of the amino molding powder of the example 2 and the amino molding powder of the comparative example 1 are weighed in a beaker, water is respectively added to form paste with the solid content of 45 percent, the paste is uniformly stirred, glue is respectively applied to the gluing surface of the poplar veneer, and the glue application amount is 250g/m on one side 2 . Then two poplar veneers are combined together in parallel along lines, the two poplar veneers are aged for 30min, hot pressing is carried out on a vulcanizing press, the hot pressing pressure is 1.1MPa, the temperature is 110 ℃, the time is 5min, the two poplar veneers are tested after being placed for 7 days, the test method refers to the corresponding test method of GB/T14074-2017, and the formaldehyde release amount test is tested according to the GB18580-2017 rule.
Results: the amino molding powder of example 2 was subjected to a perforation extraction method to determine the formaldehyde release amount of 3.4mg/100g; climatic chamber method measurement value 0.42mg/m 3 The requirement of the formaldehyde release amount E0 level of the board is met, and the bonding strength is 2.4MPa.
The amino molding powder of comparative example 1, i.e., the urea-formaldehyde resin in which the alginate does not participate in the reaction, is not preferableDispersing in water, and measuring the formaldehyde release amount by a perforation extraction method to 9.3mg/100g, wherein the formaldehyde release amount is higher; climatic chamber method measurement value 0.123mg/m 3 The E0 level requirement of the formaldehyde release amount of the plate cannot be met.
Example 3
Polycondensation reaction: under the micro negative pressure state, the formaldehyde solution pump metered by the formaldehyde metering tank
Adding into polycondensation reaction kettle, adding metered urotropine into the reaction kettle via feeding hole, and stirring
A stirrer, the PH of which is adjusted to 8.5 plus or minus 0.2. Then the reaction kettle is closed, steam is introduced into the jacket to make the reaction
The temperature in the kettle is kept at about 80 ℃, quantitative urea is added, and the closed reaction is carried out for about 90 minutes with continuous stirring
Preparing materials: the molar ratio of formaldehyde to urea is 1:1.2, and the urea is 100 parts by weight, 7 parts by weight of hexamethylenetetramine, 0.5 part by weight of ammonium chloride, 65 parts by weight of aeronautical brocade alpha-cellulose, 0.7 part by weight of lithium stearate and 25 parts by weight of oxidized sodium alginate. The specific production process comprises the following steps: (1) Pumping 37% formaldehyde solution metered by a formaldehyde metering tank into a Zheng Tang K-1000L polycondensation reaction kettle, adding metered hexamethylenetetramine into the reaction kettle through a feeding hole, starting a stirrer, adjusting the pH to be 6.6 by sodium hydroxide, heating to 60 ℃, and adding urea; (3) Sealing the reaction kettle, keeping the temperature in the reaction kettle at 60 ℃, adding oxidized sodium alginate, continuously stirring for 7min, performing condensation reaction, wherein the pH value of the condensation reaction is 6.6, the temperature is 70 ℃, and the constant-temperature reaction time is 95min, so that the product becomes a foam solid with a reticular structure, and a condensation product is obtained; (3) Conveying the condensation product to a resin intermediate tank through a closed pipeline, discharging the condensation product to a Honno NH-2000L kneader through a pipeline, adding ammonium chloride, wood pulp and lithium stearate, and kneading for 12min at a kneading temperature of 63 ℃ under a vacuum degree of-0.094 MPa; (4) drying at 60 ℃ for 1h; (6) crushing: crushing the tin epitaxy WH-400 crusher at the rotating speed of 3400 rpm; (6) ball milling; (7) sieving, sieving the powder with a 325-mesh sieve, and packaging.
Wherein oxidized sodium alginate is prepared by placing Galaxy biological sea in a reaction kettle at room temperature under light-proof condition according to weight partsDispersing 8 parts of sodium alginate in 60 parts of deionized water, adding a sodium periodate aqueous solution under the stirring condition of 300rpm, continuously adding deionized water until the water content is 100 parts, reacting for 7 hours, adding 0.3 part of salt and 50 parts of alcohol, precipitating and filtering, dissolving with deionized water, precipitating and filtering with alcohol, drying at 60 ℃ for 13 hours after filtering to obtain white oxidized sodium alginate, wherein the oxidation degree of the oxidized sodium alginate is 25% according to an iodine content measuring method, and M w 10 ten thousand, and the polydispersity is 1.8.
Performance testing of the amino molding powders of examples 1 to 3 was carried out, and the test results are shown in Table 1
TABLE 1 results of Performance test of the amino molding powders of examples 1 to 3 and comparative example 1
Note that: reference is made to GB/T14074-2017 adhesives for wood industry and resin inspection methods thereof, and to GB/T14732-2017 urea formaldehyde, phenolic and melamine formaldehyde resins for adhesives for wood industry; preparation of test specimens preheating before molding was carried out according to ISO14527-2:1999, 4.4: ISO295 was used: the preheating conditions in the drying of 7.2 in 2004. Molding of the test specimens was carried out in accordance with ISO14527-2:1999 4.4. Sample condition adjustment is in accordance with ISO14527-2:1999, 5. Flowability is in accordance with DIN53465: the measurement was performed in accordance with the method specified in 1963. Other properties were as per ISO14527-2: 1999. the specification of 6 in (2) performs performance measurement on the requirements of each performance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (5)
1. The production method of the amino molding powder comprises the conventional step of generating methylol urea by carrying out a contact addition reaction on formaldehyde and urea in a molar ratio of 1:1-1.5, and is characterized by further comprising the following steps: (1) Sealing the reaction kettle, keeping the temperature in the reaction kettle at 58-62 ℃, adding oxidized alginate accounting for 15-35 wt% of urea, continuously stirring for 5-10 min, and performing condensation reaction to obtain a netty foam-like solid with a bodily form structure, thus obtaining a condensation product; (2) Conveying the condensation product to a resin intermediate tank through a closed pipeline, discharging the condensation product to a kneader through a self-flowing pipeline, adding ammonium chloride, wood pulp and lithium stearate, and kneading for 10-15 min at a kneading temperature of 60-65 ℃; (3) drying; (4) crushing; (5) ball milling; (6) sieving and packaging.
2. The method for producing an amino molding powder according to claim 1, wherein the condition of the condensation reaction is a pH of 6.5 to 6.8, a temperature of 65 to 75 ℃ and a constant temperature reaction time of 90 to 100 minutes.
3. The method for producing an amino molding powder according to claim 1, wherein the alginate is one of sodium alginate and potassium alginate, the oxidized alginate has an oxidation degree of 15-35% according to an iodine measurement method, an Mw of 2-15 ten thousand, and a polydispersity of 1.6-2.
4. The method for producing the amino molding powder according to claim 1, wherein the drying process is performed at 60-80 ℃ for 1-2 hours.
5. The method for producing the amino molding powder according to claim 1, wherein the amount of the hexamethylenetetramine is 5-8 parts by weight, the amount of the ammonium chloride is 0.4-0.6 part by weight, the amount of the alpha-cellulose is 60-70 parts by weight, and the amount of the lithium stearate is 0.5-1 part by weight.
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