CN114214014A - Method for synthesizing urea-formaldehyde resin with ultralow formaldehyde release by using soybean protein hydrolysate - Google Patents
Method for synthesizing urea-formaldehyde resin with ultralow formaldehyde release by using soybean protein hydrolysate Download PDFInfo
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 205
- 229920001807 Urea-formaldehyde Polymers 0.000 title claims abstract description 50
- 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 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 28
- 108010073771 Soybean Proteins Proteins 0.000 title claims abstract description 24
- 239000003531 protein hydrolysate Substances 0.000 title claims abstract description 23
- 235000019710 soybean protein Nutrition 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000004202 carbamide Substances 0.000 claims abstract description 39
- 230000008569 process Effects 0.000 claims abstract description 16
- 108010009736 Protein Hydrolysates Proteins 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 238000003860 storage Methods 0.000 claims description 41
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 28
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 20
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 17
- 235000019253 formic acid Nutrition 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000011229 interlayer Substances 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 4
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 235000018102 proteins Nutrition 0.000 claims description 2
- 108090000623 proteins and genes Proteins 0.000 claims description 2
- 102000004169 proteins and genes Human genes 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- 235000010469 Glycine max Nutrition 0.000 claims 1
- 244000068988 Glycine max Species 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 20
- 230000001070 adhesive effect Effects 0.000 abstract description 20
- 239000000843 powder Substances 0.000 abstract description 11
- 239000008098 formaldehyde solution Substances 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 230000009471 action Effects 0.000 abstract description 2
- 238000007259 addition reaction Methods 0.000 abstract description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 abstract 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 abstract 1
- 235000013877 carbamide Nutrition 0.000 description 30
- 230000001276 controlling effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 8
- 230000002441 reversible effect Effects 0.000 description 6
- 238000005034 decoration Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 229920001744 Polyaldehyde Polymers 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- 150000005215 alkyl ethers Chemical group 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 238000007031 hydroxymethylation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000012432 intermediate storage Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000007065 protein hydrolysis Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 210000001533 respiratory mucosa Anatomy 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 229940001941 soy protein Drugs 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09J161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C09J161/24—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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
- C08G12/12—Ureas; Thioureas
-
- 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
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a process for synthesizing urea-formaldehyde resin with ultralow formaldehyde release by using soybean protein hydrolysate, relates to the field of high-molecular adhesives, and relates to a method for synthesizing urea-formaldehyde resin with ultralow formaldehyde release by using soybean protein hydrolysate. The invention comprises three steps: firstly, reacting high-concentration formaldehyde solution with part of urea to synthesize pre-acetal; then the urea and urea are subjected to addition and polycondensation reaction under the conditions of weak base, weak acid and weak base to synthesize urea-formaldehyde resin; finally, the urea-formaldehyde resin with ultralow formaldehyde release is synthesized by curing reaction under the action of the soybean protein hydrolysate (powder). The content of free formaldehyde in the synthesized urea-formaldehyde resin reaches the E1 standard newly issued by the state (GB18580-2017 climate box method), and ultralow formaldehyde release is realized.
Description
Technical Field
The invention relates to the field of high-molecular adhesives, and relates to a method for synthesizing urea-formaldehyde resin with ultralow formaldehyde release by using soybean protein hydrolysate.
Background
The urea-formaldehyde resin adhesive is a variety with the largest yield in thermosetting resin, is synthesized from urea and formaldehyde solution, and is one of the polymer adhesives developed and applied earlier. The urea-formaldehyde resin adhesive has the advantages of simple production process, wide raw material source, low cost, convenience in use, high initial viscosity, high bonding strength and the like, so that the urea-formaldehyde resin adhesive is widely applied to industries such as wood processing, artificial board production, paper bonding, indoor decoration and the like, along with the development of the wood industry, the dosage of the urea-formaldehyde resin adhesive is increased more and more, and the dosage of the urea-formaldehyde resin adhesive prepared by the urea-formaldehyde resin at present accounts for more than 80% of the total amount of the industrial adhesive.
The hydroxymethylation reaction of urea and formaldehyde is a reversible process, and the characteristic of the reversible reaction determines that monomer free formaldehyde always exists in a reaction system when the positive reaction and the reverse reaction reach a balance, so that the free formaldehyde can not be eliminated under the condition that other substances do not participate in the synthesis reaction. In the application process of the urea-formaldehyde resin product, part of free formaldehyde in the glue solution can be absorbed by wood, part of formaldehyde can escape in the hot pressing process of the artificial board, and the rest of formaldehyde can be retained in pores of the wood, so that the part of formaldehyde is a main source causing harm to human bodies and can be gradually diffused into the air in a longer period.
With the increasing awareness of people on indoor environmental protection and the expansion of the application field of urea-formaldehyde adhesives, the problems of urea-formaldehyde resin adhesives are also exposed, and the urea-formaldehyde resin adhesives have the disadvantages of poor water resistance, poor aging resistance, large brittleness of cured adhesive layers, especially high content of free formaldehyde, harm to human health, stimulation to eyes, skin and respiratory mucosa, and are considered to be carcinogenic substances. The formaldehyde emission amount is divided into E1, E2 and E3 internationally according to the formaldehyde emission amount, the process for producing the environment-friendly urea-formaldehyde resin adhesive in China is relatively laggard, the main defect is that free formaldehyde is released in the using process, the market share of Chinese E1 and E2 grades is less than 20%, most of the products are low-grade E3, and even poor-grade products cannot be obtained.
Some manufacturers in China utilize modifiers such as polyvinyl alcohol, melamine and the like to reduce free formaldehyde in urea-formaldehyde resin, but because addition reaction and polycondensation reaction are reversible equilibrium reaction, the elimination effect of the free formaldehyde is not good, and the limit standard of the free formaldehyde cannot be reached.
Recently, the national quality inspection bureau and the national standardization administration committee formally release revised limit on formaldehyde release in artificial boards and products thereof made of interior decoration and finishing materials (GB18580-2017), the new edition of standards improve the limit requirement on formaldehyde release, the limit value on formaldehyde release is regulated to be 0.124 mg/cubic meter, and the limit mark is E1; this means that the limit of formaldehyde release and the detection method have been in the way of international connection in China.
Patent publication No. CN1020308768 discloses a urea-formaldehyde resin with ultralow formaldehyde release and a preparation method thereof, and discloses a synthetic route which is prepared from formaldehyde, urea and long-chain prepolymer. One or more modifiers (borax, melamine, polyvinyl alcohol) according to the weak base-weak acid-weak base process route. The method introduces long-chain polyaldehyde prepolymer (glutaraldehyde self-polymerization or mixed polymerization of glutaraldehyde and glyoxal) to participate in urea-formaldehyde resin reaction, stable alkyl ether structure is generated when the prepared resin is cured, and simultaneously, free formaldehyde is replaced by residual aldehyde groups on side chains after the long-chain polyaldehyde prepolymer is reacted to promote crosslinking, so that extremely low F/U molar ratio is ensured, the prepared urea-formaldehyde resin has low free formaldehyde content, the process is simple, and the adhesive structure is good. The formaldehyde emission of the plates prepared by using the adhesive reaches a Japanese F-rate average value which is less than or equal to 0.3 mg/L.
Junyou, Zugiping at North China university, patent publication No. CN104629662B discloses a urea-formaldehyde resin adhesive with ultra-low formaldehyde release and its preparation process: firstly, adjusting the pH value of formaldehyde by using sodium hydroxide, then adding urea for reaction, dropwise adding formic acid to control the pH value of the reaction, then adjusting the pH value by using sodium hydroxide under a certain viscosity, adding hydroxymethyl cellulose, then adding aluminum sulfate for reaction, adjusting the pH value by using formic acid, then adding polyvinyl alcohol and pure water for reaction, and reducing the temperature to room temperature to obtain the urea-formaldehyde resin with ultralow formaldehyde release.
The results of the above patents mainly reduce the content of free formaldehyde in the urea resin by improving the process and adding modifiers, but the problem of free formaldehyde generated by reversible reaction in the product is not solved, the product performance is unstable, and the release of free formaldehyde is not inhibited.
Object of the Invention
The invention mainly solves the problem that the free formaldehyde in the urea-formaldehyde resin exceeds the standard, provides a set of synthesis technical scheme, not only solves the problem that the free formaldehyde in the product exceeds the standard, but also inhibits the reversible reaction of the product to generate a new formaldehyde free phenomenon, and the formaldehyde release amount of the board prepared by using the adhesive reaches the standard requirement of the limit of formaldehyde release in artificial boards of interior decoration and finishing materials and products thereof (GB 18580-2017).
Technical scheme
The invention comprises three steps: firstly, reacting 50% formaldehyde solution with urea to synthesize urea formaldehyde pre-condensed liquid, and then reacting the urea formaldehyde pre-condensed liquid with urea to synthesize urea formaldehyde resin according to a weak base-weak acid-weak base process route; and finally, adding the soybean protein hydrolysate into the urea-formaldehyde resin, and performing curing reaction to synthesize the urea-formaldehyde resin with ultralow formaldehyde release.
The method comprises the steps of firstly synthesizing a urea formaldehyde pre-shrinking solution (UFC), using the urea formaldehyde pre-shrinking solution to replace a formaldehyde solution to react with urea to synthesize a urea formaldehyde resin adhesive, wherein the urea formaldehyde pre-shrinking solution is synthesized by using formaldehyde and urea (1/4-1/2 of the molar weight of formaldehyde) with the content of 50% of the total formaldehyde and urea in a reaction kettle under the action of a catalyst (sodium hydroxide) to obtain the urea formaldehyde pre-shrinking solution; then adding the residual urea into a polymerization kettle, adjusting the pH value by using liquid alkali or formic acid, and synthesizing urea-formaldehyde resin according to a weak alkali-weak acid-weak alkali process route; and finally, adding the soybean protein hydrolysate, controlling the temperature and the reaction time, and carrying out curing reaction to synthesize the urea-formaldehyde resin with ultralow formaldehyde release.
A synthetic method of urea-formaldehyde resin with ultralow formaldehyde release comprises the following process steps:
a pre-aldol reaction zone: the system consists of a formaldehyde storage tank, a pre-condensation reactor, a urea storage tank and a liquid caustic soda storage tank; a50% concentrated formaldehyde aqueous solution is adopted, urea is industrial grade urea, 1/2-1/4 molar usage amount of formaldehyde is added, liquid caustic soda is used for adjusting the pH value to be alkaline, steam is introduced into an interlayer of a reaction kettle for heating, the temperature is controlled to be 60-90 ℃, stirring is carried out for reaction for 30-90 min, and urea formaldehyde resin pre-condensed liquid is generated.
B, polymerization reaction zone: consists of a reaction kettle, a urea storage tank and a liquid caustic soda storage tank; adding preacetal into a reaction kettle; adding urea twice according to the reaction process, wherein the dosage of the urea is 1/2-2/5 of the mol of formaldehyde, adjusting the pH value to be alkalescent by using liquid alkali, introducing steam into an interlayer of a reaction kettle for heating, controlling the temperature to be 60-95 ℃, stirring for reaction, and condensing and refluxing generated distillate through a reflux condenser; the reaction residence time is 30-90 minutes; adding formic acid, adjusting the pH of the solution to be weakly acidic, heating the interlayer steam of the reaction kettle, and controlling the temperature to be 60-95 ℃; and (3) the reaction retention time is 30-90 minutes, the reaction end point is determined according to a cloud point method, the reaction is stopped, and the pH value is adjusted to be alkalescent by using liquid alkali.
C, a curing reaction zone: a soybean protein hydrolysate (powder) storage tank and a cooking reaction kettle; adding the soybean protein hydrolysate (powder), heating by jacket steam, stirring at 60-90 ℃, and reacting for 30-60 min.
In the pre-shrinking reaction zone, the material of the pre-shrinking reaction kettle is 304/Q235-B, an interlayer and a speed reduction stirring device; the material of the storage tank is 304/Q235-B; the urea is of industrial grade, wherein the content of sulfate is less than 0.01 percent, the content of biuret is less than 0.7 percent, and the content of free ammonia is less than 0.015 percent; the formaldehyde is industrial grade, the concentration is more than or equal to 50 percent, and the formic acid is less than 0.1 percent; methanol is less than 1.5 percent, and ferrum is less than 0.0005 percent.
In the polymerization reaction zone, the material of the reaction kettle is 304/Q235-B, and the interlayer is provided with a speed reduction stirring device; the material of the storage tank is 304/Q235-B; the urea is of industrial grade, wherein the content of sulfate is less than 0.01 percent, the content of biuret is less than 0.7 percent, and the content of free ammonia is less than 0.015 percent; the acid solution is preferably formic acid aqueous solution, and the concentration of the formic acid aqueous solution is 30-60%.
In the curing reaction zone, the curing reaction kettle is made of 304/Q235-B, the reaction kettle is an interlayer and a speed-reducing stirring device; the material of the storage tank is 304/Q235-B; the liquid alkali is 30% sodium hydroxide aqueous solution;
and in the curing reaction zone, the soybean protein hydrolysate powder contains more than or equal to 95 percent of protein, less than 0.015 percent of sulfate, less than 0.005 percent of free ammonia, less than 0.0005 percent of iron and has a pH value of 7.5-11.5.
In the curing reaction zone, the adding mass of the soybean protein hydrolysate (powder) is between 0.5 and 2 percent (95 percent content).
Drawings
FIG. 1 is a block diagram of a process for synthesizing an ultra-low formaldehyde-releasing urea-formaldehyde resin, which is a schematic flow diagram for illustrating the present invention and shows only the necessary equipment for explaining the process, while other obviously required facilities such as meters, gas confluence equipment, pumps, valves, intermediate tanks, etc. are omitted.
FIG. 1 illustrates by reference numerals:
1. a formaldehyde storage tank; 2. pre-shrinking aldehyde reaction kettle; 3. a urea storage tank; 4. a liquid caustic soda storage tank; 5. a polymerization reaction kettle; 6. a formic acid storage tank; 7. a urea storage tank; 8. a liquid caustic soda storage tank; 9. a condenser; 10. soy protein hydrolysate storage tank (powder); 11. a ripening reaction kettle; 12. a product storage tank;
the invention is further described with the aid of fig. 1:
(1) the raw materials of formaldehyde, liquid caustic soda, formic acid, urea and soybean protein hydrolysate (powder) are respectively sent from storage tanks in a plant area, sent into corresponding intermediate storage tanks in a workshop, metered by a metering device according to a formula and sent into a reaction kettle.
(2) Metering formaldehyde into a pre-condensation reaction kettle R1 through a formaldehyde storage tank V1; adding the liquid caustic soda in a metering way from a liquid caustic soda storage tank V3, starting stirring, and adjusting the pH value to be 7-9; urea is metered in through a urea storage tank V2; and introducing steam into the interlayer of the reaction kettle, heating to 60-90 ℃, and controlling the reaction time to be 30-90 minutes.
(3) Pumping the reacted urea formaldehyde pre-condensed liquid into a polymerization reactor R2 by a pump, and starting stirring; adding liquid caustic soda in a liquid caustic soda storage tank V6 in a metering manner, and adjusting the pH value of the solution to 7-9; a urea storage tank V5 is used for metering and feeding urea; introducing steam into a jacket of the reaction kettle to heat, and controlling the temperature to be 60-90 ℃; and (3) enabling the reaction distillate to pass through a reflux cooler R3, and enabling the condensate to flow back into the reaction kettle for 30-90 minutes.
(4) Metering formic acid into a formic acid storage tank V4, and adjusting and controlling the pH value to be 3-6; the temperature is maintained at 60-90 ℃ for 30-90 minutes; controlling the reaction end point by a cloud point method; immediately after the end point is reached, adjusting the pH value to 7-9 by using liquid caustic soda, and stopping the reaction.
(5) Pumping the reactants into a ripening reaction kettle R4 by a pump, starting stirring, adding the soybean protein hydrolysate (powder) in a soybean protein hydrolysate (powder) storage tank V7 in a metering manner, maintaining the temperature at 60-90 ℃ for 30-60 minutes, and cooling to room temperature for discharging.
Advantageous effects
The invention provides a synthesis method of urea-formaldehyde resin with ultralow formaldehyde release, provides an effective scheme for solving the problem of high free formaldehyde content of resin products, and solves the problem that the free formaldehyde content in the urea-formaldehyde resin synthesized at present exceeds the standard, wherein the formaldehyde release amount of the board prepared by using the adhesive meets the standard requirement of the formaldehyde release limit in artificial boards and products thereof as materials for interior decoration and finishing (GB 18580-2017).
The comprehensive performance of the urea-formaldehyde resin adhesive prepared by using the soybean protein hydrolysate is detected according to GB/T9846-.
The results are shown in the table.
Detection index of main performance of UF resin
Detailed description of the preferred embodiments (examples)
The raw materials of formaldehyde, alkali liquor, formic acid, urea and soybean protein hydrolysis (powder) are respectively sent from storage tanks in a plant area, sent into corresponding storage tanks in a workshop and then metered by a metering device according to a formula and sent into a reaction kettle.
The entire system is replaced with N2 or other inert gas and the system oxygen content is detected from the exhaust emissions to be below 10 PPm.
Formaldehyde enters a pre-condensation reaction kettle R1 by passing through a formaldehyde storage tank V1 (the formaldehyde content is 50 percent) and metering 810Kg by a mass pump; starting stirring, measuring and gradually adding 2.5Kg of liquid caustic soda by a liquid caustic soda storage tank V3, and adjusting the pH value to be 7-9.5; 135Kg of urea was metered in via urea tank V2; and (3) introducing steam into the interlayer of the reaction kettle, heating to 85 ℃, reacting for 80 minutes, and cooling to below 50 ℃ for later use when the temperature is qualified.
Adding 337.5Kg of pre-polymerized urea-formaldehyde resin solution into a polymerization reactor R2 by a pump, adding 1.5Kg of liquid alkali from a storage tank V6, adjusting the pH value to 7-9, heating the steam of a kettle jacket to 90 ℃, adding 202Kg of urea from a urea storage tank V5 by a meter, cooling the distillate generated by the reaction by a reflux cooler R3, adding 3.0Kg of cooling liquid into the reaction kettle again to react for 80 minutes, adding formic acid, adding 3.0Kg of formic acid from a formic acid storage tank V4, controlling the pH value to 4.0-6.0, maintaining the temperature at 85 ℃, and reacting for 40 minutes until the reaction end point (controlling the reaction end point by a cloud point method).
The reacted materials are put into a curing reaction kettle R4, stirring is started, 10Kg of soybean protein hydrolysate (powder) is metered and added from a special storage tank V7, the heating of interlayer steam is controlled at 80 ℃, and the reaction is terminated after 50 minutes; and cooling to 40 ℃, and pumping the product into a urea-formaldehyde resin storage tank V8 for storage after the product is qualified through inspection.
Claims (4)
1. A synthetic method of urea-formaldehyde resin with ultralow formaldehyde release comprises the following process steps:
A. a pre-condensation reaction zone: the system consists of a formaldehyde storage tank, a pre-condensation reactor, a urea storage tank and a liquid caustic soda storage tank; a50% concentrated formaldehyde aqueous solution is adopted, urea is industrial grade urea, 1/2-1/4 molar weight of formaldehyde is added, liquid alkali is used for adjusting the pH value to be alkalescent, steam is introduced into an interlayer of a reaction kettle for heating, the temperature is controlled to be 60-90 ℃, stirring is carried out for reaction for 30-90 min, and urea formaldehyde resin pre-condensed liquid is generated.
B. A polymerization reaction zone: consists of a reaction kettle, a urea storage tank and a liquid caustic soda storage tank; adding preacetal into a reaction kettle; the using amount of the urea is 1/2-2/5 of the molar total amount of the formaldehyde, liquid caustic soda is used for adjusting the pH value to be alkalescent, steam is introduced into an interlayer of the reaction kettle for heating, the temperature is controlled to be 60-90 ℃, stirring reaction is carried out, and the produced distillate is condensed and refluxed by a reflux condenser; the reaction residence time is 30-90 minutes; adding formic acid, adjusting the pH of the solution to be weakly acidic, heating the interlayer steam of the reaction kettle, and controlling the temperature to be 60-90 ℃; the reaction residence time is 30-90 minutes, the reaction end point is determined according to the cloud point, the reaction is stopped, and the pH value is adjusted to be alkalescent by using liquid alkali.
C. A curing reaction zone: consists of a soybean protein hydrolysate storage tank and a cooked reaction kettle; adding the soybean protein hydrolysate, heating the soybean protein hydrolysate by introducing steam into a jacket, stirring the soybean protein hydrolysate at the temperature of 60-90 ℃ for reaction, keeping the reaction for 30-60 min, cooling the reaction product to room temperature, and discharging the product.
2. The process of claim 1, wherein: in the pre-condensation reaction zone, the urea is of industrial grade, the content of sulfate is less than 0.01 percent, the content of biuret is less than 0.7 percent, and the content of free ammonia is less than 0.015 percent; the formaldehyde is industrial grade, the concentration is more than or equal to 50 percent, and the formic acid is less than 0.1 percent; methanol is less than 1.5 percent, and ferrum is less than 0.0005 percent.
3. The process of claim 1, wherein: a curing reaction zone, wherein the content of the soybean protein hydrolysate is more than or equal to 95 percent; the content of sulfate is less than 0.015 percent, the content of free ammonia is less than 0.005 percent, the content of iron is less than 0.0005 percent, and the pH value is 7.5-11.5.
4. The process of claim 1, wherein: in the curing reaction zone, the addition amount of the soybean hydrolyzed protein is between 0.5 and 2 percent (the content of 95 percent), the reaction temperature is preferably between 60 and 90 ℃, and the reaction residence time is preferably between 30 and 60 min.
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|---|---|---|---|---|
| AU2007266778A1 (en) * | 2006-05-26 | 2007-12-06 | Chimar Hellas S.A. | Aminoplast resin of high performance for lignocellulosic materials |
| CN104629662A (en) * | 2015-02-03 | 2015-05-20 | 北华大学 | Ultralow-formaldehyde-release urea-formaldehyde resin adhesive and preparation process thereof |
| CN111333799A (en) * | 2020-03-31 | 2020-06-26 | 广西精典化工新材料有限公司 | Synthetic method of urea-formaldehyde resin with ultralow formaldehyde release |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2007266778A1 (en) * | 2006-05-26 | 2007-12-06 | Chimar Hellas S.A. | Aminoplast resin of high performance for lignocellulosic materials |
| CN104629662A (en) * | 2015-02-03 | 2015-05-20 | 北华大学 | Ultralow-formaldehyde-release urea-formaldehyde resin adhesive and preparation process thereof |
| CN111333799A (en) * | 2020-03-31 | 2020-06-26 | 广西精典化工新材料有限公司 | Synthetic method of urea-formaldehyde resin with ultralow formaldehyde release |
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