CN116769122B - Boiling water resistant amino impregnating resin and preparation method thereof - Google Patents
Boiling water resistant amino impregnating resin and preparation method thereof Download PDFInfo
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- CN116769122B CN116769122B CN202310746827.6A CN202310746827A CN116769122B CN 116769122 B CN116769122 B CN 116769122B CN 202310746827 A CN202310746827 A CN 202310746827A CN 116769122 B CN116769122 B CN 116769122B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000009835 boiling Methods 0.000 title claims abstract description 63
- 229920005989 resin Polymers 0.000 title claims abstract description 50
- 239000011347 resin Substances 0.000 title claims abstract description 50
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 152
- KCEGBPIYGIWCDH-UHFFFAOYSA-N 7,8-diaminononanoic acid Chemical compound CC(N)C(N)CCCCCC(O)=O KCEGBPIYGIWCDH-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 63
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 61
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 60
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000004202 carbamide Substances 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 29
- 238000001816 cooling Methods 0.000 claims abstract description 28
- 230000001276 controlling effect Effects 0.000 claims abstract description 14
- 238000007599 discharging Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 14
- 229920003180 amino resin Polymers 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 30
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 18
- 239000002585 base Substances 0.000 description 13
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000000123 paper Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 7
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical group C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- DFPFHJJQYOWNGX-UHFFFAOYSA-N pentadecane-3,3-diamine Chemical compound CCCCCCCCCCCCC(N)(N)CC DFPFHJJQYOWNGX-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 quaternium Chemical compound 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000036561 sun exposure Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
Classifications
-
- 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
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/34—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds and acyclic or carbocyclic compounds
- C08G12/36—Ureas; Thioureas
- C08G12/38—Ureas; Thioureas and melamines
-
- 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
- C08G12/06—Amines
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 provides boiling water resistant amino impregnating resin and a preparation method thereof, relating to the technical field of high polymer materials; the preparation method comprises the following steps: mixing formaldehyde solution A, melamine A, pentaerythritol A, 7, 8-diaminononanoic acid A and urea A, regulating pH value to be alkaline, heating to 85-95 ℃ for reaction until the reaction solution is transparent; cooling the reaction liquid to 65-85 ℃, adding formaldehyde solution B, melamine B, pentaerythritol tetraamine B, 7, 8-diamino nonanoic acid B and urea B into the reaction liquid, controlling the pH value to be alkaline, keeping the temperature for reaction until the water miscibility is 1:2-3, stopping the reaction, cooling to room temperature, and discharging. According to the preparation method of the boiling water resistant amino impregnating resin, 7, 8-diaminononanoic acid and pentaerythritol are introduced into the raw materials, so that the amino impregnating resin has excellent adhesion with a base material and excellent boiling water resistance under the condition that the mechanical property of the material is not reduced.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a boiling water resistant amino impregnating resin and a preparation method thereof.
Background
Decorative composite boards are widely used in many applications such as laminate flooring, furniture or decorative boards, and many of these composite boards are formed by bonding a base board with impregnated paper having a decorative pattern by hot pressing, and bonding the impregnated paper to the base board at a certain temperature and pressure for a certain time. The substrate based on PVC materials is now more selected: such as SPC (with PVC as base material and heavy calcium as filler), WPC (with PVC as base material and wood fiber as filler), etc. These substrates have good properties of light weight, easy processing, etc., while being free of formaldehyde contamination problems. The decorative composite board synthesized by hot pressing has the advantage of flexible decorative patterns of the decorative board, has the advantage of the base board, and can meet the requirements of different occasions.
However, due to the special nature of PVC materials, the addition of large amounts of auxiliary agents and fillers during their processing results in a lot of materials that are difficult to attach to the finished PVC, including amino resins used for impregnating the decorative paper, in particular, the decorative layer and the substrate are easily separated at the end of the hot pressing discharge, or the decorative layer and the substrate are easily separated (delaminated) when in use. Even if the two layers are not layered in a dry state, the decorative layer and the base plate are easy to be separated partially and cracked under the conditions of soaking in water, boiling in water or long-time outdoor air and sun exposure, namely, the adhesiveness is poor. At present, a layer of intermediate layer is attached to the surface of a PVC material to serve as a bridge for impregnating resin and the PVC material, and a high polymer intermediate layer is introduced by CN 113667415A, so that the PVC material has a good effect, but is complex in operation and process.
In view of the problem that the amino-impregnated decorative board has poor adhesion after boiling, developing a boiling water resistant amino-impregnated resin is a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to solve the technical problems that: in order to solve the problem of poor adhesion of an amino-impregnated decorative board after water boiling in the prior art, the invention provides a preparation method of boiling water resistant amino-impregnated resin, which introduces 7, 8-diaminononanoic acid and pentaerythritol into raw materials, so that the amino-impregnated decorative board has excellent boiling water resistance under the condition of not reducing the mechanical properties of the materials, and still has excellent adhesion with a base material after water boiling, thereby solving the problem of poor adhesion of the amino-impregnated decorative board after water boiling in the prior art.
The technical scheme adopted for solving the technical problems is as follows:
a method for preparing boiling water resistant amino impregnating resin, which comprises the following steps:
s1: mixing formaldehyde solution A, melamine A, pentaerythritol A, 7, 8-diaminononanoic acid A and urea A, regulating pH value to be alkaline, heating to 85-95 ℃ for reaction until the reaction solution is transparent;
s2: cooling the reaction liquid to 65-85 ℃, adding formaldehyde solution B, melamine B, pentaerythritol tetraamine B, 7, 8-diaminononanoic acid B and urea B into the reaction liquid, controlling the pH value to be alkaline, keeping the temperature for reaction until the water miscibility is 1:2-3, stopping the reaction, cooling to room temperature, discharging, and obtaining the boiling water resistant amino impregnating resin.
Alternatively, the formaldehyde solution A and the formaldehyde solution B are 37wt% formaldehyde aqueous solutions.
Optionally, in step S1, the formaldehyde solution a, the melamine a, the pentaerythritol a, the 7, 8-diaminononanoic acid a, and the urea a are used in a ratio of (162-203) g: (0.4-0.5) mol: (0.1-0.2) mol: (0.1-0.12) mol: (0.2-0.25) mol.
Optionally, in step S2, the formaldehyde solution B, the melamine B, the pentaerythritol B, the 7, 8-diaminononanoic acid B, and the urea B are used in a ratio of (122-162) g: (0.3-0.4) mol: (0.2-0.3) mol: (0.18-0.2) mol: (0.25-0.3) mol.
Optionally, in step S1, the pH is adjusted to 8.5-9.5.
Optionally, the pH value of the step S1 is adjusted to 8.5-9.5 by alkali liquor.
Alternatively, the lye is a 30wt% aqueous sodium hydroxide solution.
Optionally, step S2 controls the pH to be not lower than 8.5.
It is another object of the present invention to provide a boiling water resistant amino-impregnated resin prepared by the method for preparing a boiling water resistant amino-impregnated resin as described above.
The beneficial effects of the invention are as follows:
according to the preparation method of the boiling water resistant amino impregnating resin, 7, 8-diaminononanoic acid and the quaternary tetramine are introduced into the raw materials, wherein the side group of the 7, 8-diaminononanoic acid contains a polar heteroatom structure-carboxyl, so that the adhesiveness to a substrate can be greatly improved, and meanwhile, the quaternary tetramine has higher functionality and can provide excellent mechanical properties for the material; the invention not only has excellent adhesion with the base material, but also has excellent boiling water resistance under the condition of not reducing the mechanical property of the material by combining and using the 7, 8-diamino nonanoic acid and the pentaerythritol, thereby having excellent adhesion with the base material after boiling.
Detailed Description
The present invention will now be described in further detail. The embodiments described below are exemplary and intended to illustrate the invention and should not be construed as limiting the invention, as all other embodiments, based on which a person of ordinary skill in the art would obtain without inventive faculty, are within the scope of the invention.
In order to solve the problem of poor adhesiveness of amino-impregnated decorative boards after boiling in the prior art, the invention provides a preparation method of boiling water resistant amino-impregnated resin, which comprises the following steps:
s1: mixing formaldehyde solution A, melamine A, pentaerythritol A, 7, 8-diaminononanoic acid A and urea A, regulating pH value to be alkaline, heating to 85-95 ℃ for reaction until the reaction solution is transparent;
s2: cooling the reaction liquid to 65-85 ℃, adding formaldehyde solution B, melamine B, pentaerythritol tetraamine B, 7, 8-diaminononanoic acid B and urea B into the reaction liquid, controlling the pH value to be alkaline, carrying out heat preservation reaction until the water miscibility is 1:2-3, stopping the reaction, cooling to room temperature, and discharging to obtain the boiling water resistant amino impregnating resin.
According to the preparation method of the boiling water resistant amino impregnating resin, 7, 8-diaminononanoic acid and the quaternary tetramine are introduced into the raw materials, wherein the side group of the 7, 8-diaminononanoic acid contains a polar heteroatom structure-carboxyl, so that the adhesiveness to a substrate can be greatly improved, and meanwhile, the quaternary tetramine has higher functionality and can provide excellent mechanical properties for the material; the invention not only has excellent adhesion with the base material, but also has excellent boiling water resistance under the condition of not reducing the mechanical property of the material by combining and using the 7, 8-diamino nonanoic acid and the pentaerythritol, thereby having excellent adhesion with the base material after boiling.
In addition, the currently commonly used amino resin is mainly melamine formaldehyde resin, and has certain rigidity due to triazine ring in the melamine molecular structure; in addition, the condensation mechanism can also show that a three-dimensional reticular structure adhesive layer is formed after curing, triazine rings are connected with each other through methylene or ether bonds, six active hydrogens exist in the melamine molecular structure, and the defects of high crosslinking density, large internal stress, brittle adhesive layer and the like of the melamine resin after curing are caused; the 7, 8-diamino nonanoic acid introduced by the invention has lower functionality and larger side group in the molecular structure, is beneficial to reducing the crosslinking density during the polycondensation reaction, is beneficial to improving the toughness, and simultaneously is beneficial to further improving the adhesion of a substrate; meanwhile, mechanical properties such as wear resistance and the like of the material are improved by combining the pentaerythritol, so that the toughness, the wear resistance and the like of the material can be improved while the boiling water resistance and the adhesion of the material are improved.
Furthermore, the preparation method provided by the invention adopts a step-by-step feeding method, and the first step of feeding ensures that the polycondensation reaction of the raw materials of each component can be fully carried out, the crosslinking density of the resin is proper, and the synthesis of seeds is focused; and the second step of feeding reaction further promotes chain growth based on the first step of reaction, focuses on chain extension reaction, reasonably balances the proportion of all raw material components and effectively gives consideration to the comprehensive performance of the material.
In order to achieve the boiling water resistance, adhesion resistance and mechanical properties of the material, the formaldehyde solution A and the formaldehyde solution B are preferably 37 weight percent formaldehyde aqueous solutions; preferably, in the step S1, the dosage ratio of the formaldehyde solution A, the melamine A, the pentaerythritol A, the 7, 8-diaminononanoic acid A and the urea A is (162-203) g: (0.4-0.5) mol: (0.1-0.2) mol: (0.1-0.12) mol: (0.2-0.25) mol; preferably, in the step S2, the dosage ratio of the formaldehyde solution B, the melamine B, the pentaerythritol B, the 7, 8-diaminononanoic acid B and the urea B is (122-162 g): (0.3-0.4) mol: (0.2-0.3) mol: (0.18-0.2) mol: (0.25-0.3) mol.
In order to ensure that the reaction proceeds smoothly, it is preferred according to the invention that the pH value in step S1 is adjusted to 8.5-9.5, and in particular that step S1 is adjusted to 8.5-9.5 by means of an alkaline solution, preferably 30% by weight aqueous sodium hydroxide solution.
In the preferred embodiment of the invention, the pH value is controlled to be not lower than 8.5 in the step S2.
It is another object of the present invention to provide a boiling water resistant amino-impregnated resin prepared by the method of preparing a boiling water resistant amino-impregnated resin as described above.
According to the boiling water resistant amino impregnating resin provided by the invention, 7, 8-diaminononanoic acid and the quaternary tetramine are introduced into the preparation raw materials, wherein the side group of the 7, 8-diaminononanoic acid contains a polar heteroatom structure-carboxyl, so that the adhesiveness to a substrate can be greatly improved, and meanwhile, the quaternary tetramine has higher functionality and can provide excellent mechanical properties for the material; the invention not only has excellent adhesion with the base material, but also has excellent boiling water resistance under the condition of not reducing the mechanical property of the material by combining and using the 7, 8-diamino nonanoic acid and the pentaerythritol, thereby having excellent adhesion with the base material after boiling.
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of embodiments of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
Example 1
The embodiment provides a preparation method of boiling water resistant amino impregnating resin, which comprises the following steps:
s1: adding 37wt% of formaldehyde aqueous solution A, melamine A, pentaerythritol tetraamine A, 7, 8-diaminononanoic acid A and urea A into a three-neck flask provided with a condensing reflux device, adjusting the pH value to 9 by using 30wt% of sodium hydroxide aqueous solution, fully stirring, heating to 90 ℃ and reacting until the reaction solution is transparent;
wherein the dosage ratio of 37 weight percent of formaldehyde aqueous solution A, melamine A, pentaerythritol tetraamine A, 7, 8-diamino nonanoic acid A and urea A is 186g:0.45mol:0.15mol:0.12mol:0.22mol;
s2: cooling to 75 ℃, adding 37wt% of formaldehyde aqueous solution B, melamine B, pentaerythritol tetraamine B, 7, 8-diaminononanoic acid B and urea B into the reaction solution, controlling the pH value to be not lower than 8.5 during the period, keeping the temperature for reaction until the water miscibility is 1:3, stopping the reaction, cooling to room temperature, discharging to obtain boiling water resistant amino impregnating resin;
wherein the dosage ratio of 37 weight percent of formaldehyde aqueous solution B, melamine B, pentaerythritol tetraamine B, 7, 8-diamino nonanoic acid B and urea B is 138g:0.35mol:0.25mol:0.18mol:0.28mol.
The infrared data are as follows: 3372cm -1 : active hydrogen (-OH, -NH-) broad peaks exist; 1662cm -1 : amide-c=o present; 1760cm -1 : carboxyl-c=o present; 1162cm -1 : -C-O-C-presence; 1557cm -1 、1360cm -1 、812cm -1 : triazine rings are present; 1720cm -1 : aldehyde-c=o is absent; 1667cm -1 ：-NH 2 Is not present.
In this example, the total amount of 37% by weight aqueous formaldehyde solution, melamine, pentaerythritol, 7, 8-diaminononanoic acid and urea was 325g:0.8mol:0.4mol:0.3mol:0.5mol.
Example 2
The embodiment provides a preparation method of boiling water resistant amino impregnating resin, which comprises the following steps:
s1: adding 37wt% of formaldehyde aqueous solution A, melamine A, pentaerythritol tetraamine A, 7, 8-diaminononanoic acid A and urea A into a three-neck flask provided with a condensing reflux device, adjusting the pH value to 9 by using 30wt% of sodium hydroxide aqueous solution, fully stirring, heating to 90 ℃ and reacting until the reaction solution is transparent;
wherein the dosage ratio of 37 weight percent of formaldehyde aqueous solution A, melamine A, pentaerythritol tetraamine A, 7, 8-diamino nonanoic acid A and urea A is 186g:0.5mol:0.2mol:0.1mol:0.2mol;
s2: cooling to 75 ℃, adding 37wt% of formaldehyde aqueous solution B, melamine B, pentaerythritol tetraamine B, 7, 8-diaminononanoic acid B and urea B into the reaction solution, controlling the pH value to be not lower than 8.5 during the period, keeping the temperature for reaction until the water miscibility is 1:3, stopping the reaction, cooling to room temperature, discharging to obtain boiling water resistant amino impregnating resin;
wherein the dosage ratio of 37 weight percent of formaldehyde aqueous solution B, melamine B, pentaerythritol tetraamine B, 7, 8-diamino nonanoic acid B and urea B is 138g:0.3mol:0.2mol:0.2mol:0.3mol.
The infrared data are as follows: 3372cm -1 : active hydrogen (-OH, -NH-) broad peaks exist; 1662cm -1 : amide-c=o present; 1760cm -1 : carboxyl-c=o present; 1162cm -1 : -C-O-C-presence; 1557cm -1 、1360cm -1 、812cm -1 : triazine rings are present; 1720cm -1 : aldehyde-c=o is absent; 1667cm -1 ：-NH 2 Is not present.
In this example, the total amount of 37% by weight aqueous formaldehyde solution, melamine, pentaerythritol, 7, 8-diaminononanoic acid and urea was 325g:0.8mol:0.4mol:0.3mol:0.5mol.
Example 3
The embodiment provides a preparation method of boiling water resistant amino impregnating resin, which comprises the following steps:
s1: adding 37wt% of formaldehyde aqueous solution A, melamine A, pentaerythritol tetraamine A, 7, 8-diaminononanoic acid A and urea A into a three-neck flask provided with a condensing reflux device, adjusting the pH value to 9 by using 30wt% of sodium hydroxide aqueous solution, fully stirring, heating to 90 ℃ and reacting until the reaction solution is transparent;
the dosage ratio of 37wt% of formaldehyde aqueous solution A, melamine A, pentaerythritol tetraamine A, 7, 8-diaminononanoic acid A and urea A is 186g:0.4mol:0.1mol:0.12mol:0.25mol;
s2: cooling to 75 ℃, adding 37wt% of formaldehyde aqueous solution B, melamine B, pentaerythritol tetraamine B, 7, 8-diaminononanoic acid B and urea B into the reaction solution, controlling the pH value to be not lower than 8.5 during the period, keeping the temperature for reaction until the water miscibility is 1:3, stopping the reaction, cooling to room temperature, discharging to obtain boiling water resistant amino impregnating resin;
the dosage ratio of 37wt% of formaldehyde aqueous solution B, melamine B, pentaerythritol tetraamine B, 7, 8-diamino nonanoic acid B and urea B is 138g:0.4mol:0.3mol:0.18mol:0.25mol.
The infrared data are as follows: 3372cm -1 : active hydrogen (-OH, -NH-) broad peaks exist; 1662cm -1 : amide-c=o present; 1760cm -1 : carboxyl-c=o present; 1162cm -1 : -C-O-C-presence; 1557cm -1 、1360cm -1 、812cm -1 : triazine rings are present; 1720cm -1 : aldehyde-c=o is absent; 1667cm -1 ：-NH 2 Is not present.
In this example, the total amount of 37% by weight aqueous formaldehyde solution, melamine, pentaerythritol, 7, 8-diaminononanoic acid and urea was 325g:0.8mol:0.4mol:0.3mol:0.5mol.
Example 4
The embodiment provides a preparation method of boiling water resistant amino impregnating resin, which comprises the following steps:
s1: adding 37wt% of formaldehyde aqueous solution A, melamine A, pentaerythritol tetraamine A, 7, 8-diaminononanoic acid A and urea A into a three-neck flask provided with a condensing reflux device, adjusting the pH value to 9 by using 30wt% of sodium hydroxide aqueous solution, fully stirring, heating to 90 ℃ and reacting until the reaction solution is transparent;
37wt% of formaldehyde aqueous solution A, melamine A, pentaerythritol A, 7, 8-diaminononanoic acid A and urea A are used in an amount ratio of 162g:0.45mol:0.15mol:0.12mol:0.22mol;
s2: cooling to 75 ℃, adding 37wt% of formaldehyde aqueous solution B, melamine B, pentaerythritol tetraamine B, 7, 8-diaminononanoic acid B and urea B into the reaction solution, controlling the pH value to be not lower than 8.5 during the period, keeping the temperature for reaction until the water miscibility is 1:3, stopping the reaction, cooling to room temperature, discharging to obtain boiling water resistant amino impregnating resin;
37wt% aqueous formaldehyde solution B, melamine B, pentaerythritol B, 7, 8-diaminononanoic acid B, urea B in a proportion of 122g:0.35mol:0.25mol:0.18mol:0.28mol.
The infrared data are as follows: 3372cm -1 : active hydrogen (-OH, -NH-) broad peaks exist; 1662cm -1 : amide-c=o present; 1760cm -1 : carboxyl-c=o present; 1162cm -1 : -C-O-C-presence; 1557cm -1 、1360cm -1 、812cm -1 : triazine rings are present; 1720cm -1 : aldehyde-c=o is absent; 1667cm -1 ：-NH 2 Is not present.
In this example, the total amount of 37% by weight aqueous formaldehyde solution, melamine, pentaerythritol, 7, 8-diaminononanoic acid and urea was 284g:0.8mol:0.4mol:0.3mol:0.5mol.
Example 5
The embodiment provides a preparation method of boiling water resistant amino impregnating resin, which comprises the following steps:
s1: adding 37wt% of formaldehyde aqueous solution A, melamine A, pentaerythritol tetraamine A, 7, 8-diaminononanoic acid A and urea A into a three-neck flask provided with a condensing reflux device, adjusting the pH value to 9 by using 30wt% of sodium hydroxide aqueous solution, fully stirring, heating to 90 ℃ and reacting until the reaction solution is transparent;
wherein the dosage ratio of 37 weight percent of formaldehyde aqueous solution A, melamine A, pentaerythritol tetraamine A, 7, 8-diamino nonanoic acid A and urea A is 203g:0.45mol:0.15mol:0.12mol:0.22mol;
s2: cooling to 75 ℃, adding 37wt% of formaldehyde aqueous solution B, melamine B, pentaerythritol tetraamine B, 7, 8-diaminononanoic acid B and urea B into the reaction solution, controlling the pH value to be not lower than 8.5 during the period, keeping the temperature for reaction until the water miscibility is 1:3, stopping the reaction, cooling to room temperature, discharging to obtain boiling water resistant amino impregnating resin;
37wt% of formaldehyde aqueous solution B, melamine B, pentaerythritol tetraamine B, 7, 8-diamino nonanoic acid B and urea B with the dosage ratio of 162g:0.35mol:0.25mol:0.18mol:0.28mol.
The infrared data are as follows: 3372cm -1 : active hydrogen (-OH, -NH-) broad peaks exist; 1662cm -1 : amide-c=o present; 1760cm -1 : carboxyl-c=o present; 1162cm -1 : -C-O-C-presence; 1557cm -1 、1360cm -1 、812cm -1 : triazine rings are present; 1720cm -1 : aldehyde-c=o is absent; 1667cm -1 ：-NH 2 Is not present.
In this example, the total amount of 37% by weight aqueous formaldehyde solution, melamine, pentaerythritol, 7, 8-diaminononanoic acid and urea was 365g:0.8mol:0.4mol:0.3mol:0.5mol.
Example 6
The embodiment provides a preparation method of boiling water resistant amino impregnating resin, which comprises the following steps:
s1: adding 37wt% of formaldehyde aqueous solution A, melamine A, pentaerythritol tetraamine A, 7, 8-diaminononanoic acid A and urea A into a three-neck flask provided with a condensing reflux device, adjusting the pH value to 9.5 by using 30wt% of sodium hydroxide aqueous solution, fully stirring, heating to 85 ℃ and reacting until the reaction solution is transparent;
the dosage ratio of 37wt% of formaldehyde aqueous solution A, melamine A, pentaerythritol tetraamine A, 7, 8-diaminononanoic acid A and urea A is 186g:0.45mol:0.15mol:0.12mol:0.22mol;
s2: cooling to 65 ℃, adding 37wt% of formaldehyde aqueous solution B, melamine B, pentaerythritol tetraamine B, 7, 8-diaminononanoic acid B and urea B into the reaction solution, controlling the pH value to be not lower than 8.5 during the period, keeping the temperature for reaction until the water miscibility is 1:2, stopping the reaction, cooling to room temperature, discharging to obtain boiling water resistant amino impregnating resin;
the dosage ratio of 37wt% of formaldehyde aqueous solution B, melamine B, pentaerythritol tetraamine B, 7, 8-diamino nonanoic acid B and urea B is 138g:0.35mol:0.25mol:0.18mol:0.28mol.
The infrared data are as follows: 3372cm -1 : active hydrogen (-OH, -NH-) broad peaks exist; 1662cm -1 : amide-c=o present; 1760cm -1 : carboxyl-c=o present; 1162cm -1 : -C-O-C-presence; 1557cm -1 、1360cm -1 、812cm -1 : triazine rings are present; 1720cm -1 : aldehyde-c=o is absent; 1667cm -1 ：-NH 2 Is not present.
In this example, the total amount of 37% by weight aqueous formaldehyde solution, melamine, pentaerythritol, 7, 8-diaminononanoic acid and urea was 325g:0.8mol:0.4mol:0.3mol:0.5mol.
Example 7
The embodiment provides a preparation method of boiling water resistant amino impregnating resin, which comprises the following steps:
s1: adding 37wt% of formaldehyde aqueous solution A, melamine A, pentaerythritol tetraamine A, 7, 8-diaminononanoic acid A and urea A into a three-neck flask provided with a condensing reflux device, adjusting the pH value to 8.5 by using 30wt% of sodium hydroxide aqueous solution, fully stirring, heating to 95 ℃ and reacting until the reaction solution is transparent;
the dosage ratio of 37wt% of formaldehyde aqueous solution A, melamine A, pentaerythritol tetraamine A, 7, 8-diaminononanoic acid A and urea A is 186g:0.45mol:0.15mol:0.12mol:0.22mol;
s2: cooling to 85 ℃, adding 37wt% of formaldehyde aqueous solution B, melamine B, pentaerythritol tetraamine B, 7, 8-diaminononanoic acid B and urea B into the reaction solution, controlling the pH value to be not lower than 8.5 during the period, keeping the temperature for reaction until the water miscibility is 1:2, stopping the reaction, cooling to room temperature, discharging to obtain boiling water resistant amino impregnating resin;
the dosage ratio of 37wt% of formaldehyde aqueous solution B, melamine B, pentaerythritol tetraamine B, 7, 8-diamino nonanoic acid B and urea B is 138g:0.35mol:0.25mol:0.18mol:0.28mol.
The infrared data are as follows: 3372cm -1 : active hydrogen (-OH, -NH-) broad peaks exist; 1662cm -1 : amide-c=o present; 1760cm -1 : carboxyl-c=o present; 1162cm -1 : -C-O-C-presence; 1557cm -1 、1360cm -1 、812cm -1 : triazine rings are present; 1720cm -1 : aldehyde-c=o is absent; 1667cm -1 ：-NH 2 Is not present.
In this example, the total amount of 37% by weight aqueous formaldehyde solution, melamine, pentaerythritol, 7, 8-diaminononanoic acid and urea was 325g:0.8mol:0.4mol:0.3mol:0.5mol.
The following comparative examples are all compared to example 1:
comparative example 1
The comparative example provides a method for preparing amino impregnating resin, comprising the following steps:
s1: adding 37wt% of formaldehyde aqueous solution A, melamine A, pentaerythritol A and urea A into a three-neck flask with a condensing reflux device, adjusting the pH value to 9 by using 30wt% of sodium hydroxide aqueous solution, fully stirring, heating to 90 ℃ and reacting until the reaction solution is transparent;
the dosage ratio of 37wt% of formaldehyde aqueous solution A, melamine A, pentaerythritol tetraamine A and urea A is 186g:0.45mol:0.15mol:0.34mol;
s2: cooling to 75 ℃, adding 37wt% of formaldehyde aqueous solution B, melamine B, pentaerythritol B and urea B into the reaction solution, controlling the pH value to be not lower than 8.5 during the period, carrying out heat preservation reaction until the water miscibility is 1:3, stopping the reaction, cooling to room temperature, and discharging to obtain amino-impregnated resin;
the dosage ratio of 37wt% of formaldehyde aqueous solution B, melamine B, pentaerythritol tetraamine B, 7, 8-diamino nonanoic acid B and urea B is 138g:0.35mol:0.25mol:0.46mol.
The infrared data are as follows: 3372cm -1 : active hydrogen (-OH, -NH-) broad peaks exist; 1662cm -1 : amide-c=o present; 1162cm -1 : -C-O-C-presence; 1557cm -1 、1360cm -1 、812cm -1 : triazine rings are present; 1720cm -1 : aldehyde-c=o is absent; 1667cm -1 ：-NH 2 Is not present.
Comparative example 2
This comparative example differs from example 1 in that 7, 8-diaminononanoic acid was replaced by ethylenediamine.
Comparative example 3
This comparative example differs from example 1 in that 7, 8-diaminononanoic acid was replaced by 1, 9-nonanediamine.
Comparative example 4
This comparative example differs from example 1 in that 7, 8-diaminononanoic acid was replaced by dodecylpropanediamine.
Comparative example 5
The comparative example provides a method for preparing amino impregnating resin, comprising the following steps:
s1: adding 37wt% of formaldehyde aqueous solution A, melamine A, 7, 8-diamino nonanoic acid A and urea A into a three-neck flask with a condensing reflux device, adjusting the pH value to 9 by using 30wt% of sodium hydroxide aqueous solution, fully stirring, heating to 90 ℃ and reacting until the reaction solution is transparent;
the dosage ratio of 37wt% of formaldehyde aqueous solution A, melamine A, 7, 8-diamino nonanoic acid A and urea A is 186g:0.6mol:0.12mol:0.22mol;
s2: cooling to 75 ℃, adding 37wt% of formaldehyde aqueous solution B, melamine B, 7, 8-diamino nonanoic acid B and urea B into the reaction solution, controlling the pH value to be not lower than 8.5 during the period, keeping the temperature for reaction until the water miscibility is 1:3, stopping the reaction, cooling to room temperature, discharging to obtain amino-impregnated resin;
the dosage ratio of 37wt% of formaldehyde aqueous solution B, melamine B, 7, 8-diamino nonanoic acid B and urea B is 138g:0.6mol:0.18mol:0.28mol.
The infrared data are as follows: 3372cm -1 : active hydrogen (-OH, -NH-) broad peaks exist; 1662cm -1 : amide-c=o present; 1760cm -1 : carboxyl-c=o present; 1162cm -1 : -C-O-C-presence; 1557cm -1 、1360cm -1 、812cm -1 : triazine rings are present; 1720cm -1 : aldehyde-c=o is absent; 1667cm -1 ：-NH 2 Is not present.
Comparative example 6
The comparative example provides a method for preparing amino impregnating resin, comprising the following steps:
sequentially adding 37wt% of formaldehyde aqueous solution, melamine, pentaerythritol, 7, 8-diaminononanoic acid and urea into a three-neck flask provided with a condensing reflux device, adjusting the pH value to 9 by using 30wt% of sodium hydroxide aqueous solution, fully stirring, heating to 90 ℃, reacting and preserving heat for 4 hours; cooling to 75 ℃, controlling the pH value to be not lower than 8.5 during the period, keeping the temperature, reacting until the water miscibility is 1:3, stopping the reaction, cooling to room temperature, discharging to obtain amino-impregnated resin;
37wt% aqueous formaldehyde solution, melamine, quaternium, 7, 8-diamino nonanoic acid and urea in an amount ratio of 325g:0.8mol:0.4mol:0.3mol:0.5mol;
the infrared data are as follows: 3372cm -1 : active hydrogen (-OH, -NH-) broad peaks exist; 1662cm -1 : amide-c=o present; 1760cm -1 : carboxyl-c=o present; 1162cm -1 : -C-O-C-presence; 1557cm -1 、1360cm -1 、812cm -1 : triazine rings are present; 1720cm -1 : aldehyde-c=o is absent; 1667cm -1 ：-NH 2 Is not present.
The boiling water resistant amino impregnating resin prepared by the invention can be applied to coating preparation of impregnated paper decorative boards.
The amino-impregnating resins prepared in the examples and comparative examples of the present invention were used to prepare impregnated paper decorative sheets as follows:
the amino-impregnating resins obtained in examples 1 to 7 and comparative examples 1 to 6 were dip-coated on the laminate by a direct dip-sizing coating method, respectively, to prepare impregnated paper decorative sheets; the drying box adopts hot air circulation, and the temperature of the drying oven is 60 ℃ so as to uniformly dry the gummed paper. Each laminated board consists of three kraft papers, the sizing amount is 80% (relative to the mass of the kraft papers), finally, PVC films are coated, and the hot pressing adopts a cold inlet and cold outlet technology, the temperature is 115 ℃, the unit pressure is 10MPa, and the time is 30min. The hot-pressed decorative board has smooth appearance, uniform color and glossiness, and no defects of dry and wet flowers, indentation, stain and the like.
The physical properties of the impregnated paper decorative sheets prepared in each example and comparative example were tested according to the following test methods, respectively:
(1) Appearance, solids content, pH, free formaldehyde test method: the test was carried out as described in GB/T14732-2017.
(2) Viscosity: at 20℃the test was performed using a paint-4 # cup.
(3) Tensile strength, elastic modulus, elongation at break test method: the test was carried out as described in GB/T7911-2013.
(4) Abrasion resistance: the grinding wheel CS-10F was loaded into a Talber abrasion test apparatus according to ASTM D1044-19, and the sample was rotated 500 revolutions under an applied load of 500 g. The haze of the sample was measured before and after the test, and the change in haze (Δh) was obtained. The method for expressing the wear resistance comprises the following steps: ΔH is less than or equal to 5.0: good wear resistance, noted "3";5.0 < DeltaH < 10.0: poor wear resistance, noted "2"; ΔH is not less than 10.0: the abrasion resistance was extremely poor, and was designated as "1".
(5) Boiling water resistance (water absorption): test pieces were prepared according to GB/T7911-2013 standard, no less than 3 samples per group.
(6) Adhesion: boiling in boiling water for more than 3 hours, wherein the amino resin impregnated paper is not separated from the substrate, and the defects of bubbling, cracking and the like on the surface of the decorative composite board are avoided, and the mark is OK; otherwise, it is denoted as "NG".
The test results are shown in Table 1:
TABLE 1
As can be seen from the data in examples 1-7 and comparative examples 1-6 of Table 1, the boiling water resistant amino-impregnated resins prepared in the examples of the present invention have excellent mechanical properties, abrasion resistance, boiling water resistance and adhesion. One of the reasons for this is that the raw material 7, 8-diaminononanoic acid has lower functionality and larger side group, has plasticizing effect, is beneficial to improving toughness, and simultaneously has a certain improvement on the adhesion of the substrate; the second reason is that the side group of the 7, 8-diamino nonanoic acid contains a polar heteroatom structure, so that the adhesion to a substrate can be greatly improved; and the third and the quaternary tetramine have higher functionality and can provide mechanical properties such as wear resistance and the like for materials.
As can be observed from examples 1-7 and comparative example 6, the stepwise addition preparation process of the boiling water resistant amino impregnating resin provided by the invention has better mechanical properties than the one-step preparation process, because the amino resin is distributed more uniformly in the soft and hard segments.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (6)
1. The preparation method of the boiling water resistant amino impregnating resin is characterized by comprising the following steps:
s1: mixing formaldehyde solution A, melamine A, pentaerythritol A, 7, 8-diaminononanoic acid A and urea A, regulating pH value to be alkaline, heating to 85-95 ℃ for reaction until the reaction solution is transparent;
s2: cooling the reaction liquid to 65-85 ℃, adding formaldehyde solution B, melamine B, pentaerythritol tetraamine B, 7, 8-diaminononanoic acid B and urea B into the reaction liquid, controlling the pH value to be alkaline, keeping the temperature for reaction until the water miscibility is 1:2-3, stopping the reaction, cooling to room temperature, discharging to obtain boiling water resistant amino impregnating resin;
the formaldehyde solution A and the formaldehyde solution B are 37wt% formaldehyde aqueous solutions; in the step S1, the dosage ratio of the formaldehyde solution A, the melamine A, the pentaerythritol A, the 7, 8-diaminononanoic acid A and the urea A is (162-203) g: (0.4-0.5) mol: (0.1-0.2) mol: (0.1-0.12) mol: (0.2-0.25) mol;
in the step S2, the dosage ratio of the formaldehyde solution B, the melamine B, the pentaerythritol B, the 7, 8-diaminononanoic acid B and the urea B is (122-162) g: (0.3-0.4) mol: (0.2-0.3) mol: (0.18-0.2) mol: (0.25-0.3) mol.
2. The method for preparing a boiling water resistant amino resin as claimed in claim 1, wherein the pH is adjusted to 8.5 to 9.5 in step S1.
3. The method for preparing a boiling water resistant amino-impregnated resin according to claim 2, wherein step S1 is performed by adjusting pH to 8.5-9.5 with alkali solution.
4. A method of preparing a boiling water resistant amino resin as claimed in claim 3, wherein the lye is 30wt% aqueous sodium hydroxide.
5. The method for preparing a boiling water resistant amino-impregnated resin according to claim 2, wherein step S2 controls pH to not lower than 8.5.
6. A boiling water resistant amino resin as claimed in any one of claims 1 to 5, characterised in that it is prepared by a process for the preparation of a boiling water resistant amino resin.
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| JP2000143751A (en) * | 1998-11-13 | 2000-05-26 | Showa Highpolymer Co Ltd | Production of low-formaldehyde amino resin |
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| CN104893633A (en) * | 2015-05-25 | 2015-09-09 | 西南林业大学 | Melamine-urea-formaldehyde copolycondensation resin adhesive for laminated wood and preparation method thereof |
| CN105949416A (en) * | 2016-06-16 | 2016-09-21 | 浙江农林大学 | Quaternary copolymerized melamine-impregnated resin adhesive and preparation method thereof |
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|---|---|---|---|---|
| JP2000143751A (en) * | 1998-11-13 | 2000-05-26 | Showa Highpolymer Co Ltd | Production of low-formaldehyde amino resin |
| CN102181027A (en) * | 2011-04-01 | 2011-09-14 | 北京联合大学生物化学工程学院 | Melamine formaldehyde resin modified by biomass materials and preparation method thereof |
| CN104513582A (en) * | 2013-09-29 | 2015-04-15 | 青岛市首胜实业有限公司 | Intumescent amino resin fireproof varnish |
| CN104893633A (en) * | 2015-05-25 | 2015-09-09 | 西南林业大学 | Melamine-urea-formaldehyde copolycondensation resin adhesive for laminated wood and preparation method thereof |
| CN105949416A (en) * | 2016-06-16 | 2016-09-21 | 浙江农林大学 | Quaternary copolymerized melamine-impregnated resin adhesive and preparation method thereof |
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