CN116478351A - Environment-friendly modified light-color phenolic resin and preparation method thereof - Google Patents
Environment-friendly modified light-color phenolic resin and preparation method thereof Download PDFInfo
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Abstract
The invention provides an environment-friendly modified light-colored phenolic resin and a preparation method thereof, relating to the technical field of high polymer materials; the preparation method comprises the following steps: mixing a functional monomer with phenol, formaldehyde solution and ammonia water, heating to 80-90 ℃, reacting for 1-2 hours, heating to 85-95 ℃, decompressing and removing water and ammonia water under 0.03-0.04MPa, and reacting for 2-4 hours to obtain the environment-friendly modified light-color phenolic resin; the molecular structure of the functional monomer contains thiourea structure and epoxy structure. According to the preparation method, the functional monomer with the thiourea structure and the epoxy structure is introduced, and the thiourea structure and the epoxy structure can both act with the phenolic group to prevent the phenolic group from being oxidized into quinone, so that the preparation method provided by the invention has the effect of high-efficiency decolorization, and is beneficial to obtaining light-color phenolic resin; the light-colored phenolic resin is obtained by the functional monomer through a chemical synthesis modification method, which is beneficial to improving the decolorization durability.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an environment-friendly modified light-color phenolic resin and a preparation method thereof.
Background
Phenolic resins are widely used in the production of water-resistant plywood and faced artificial boards, and in the preparation of electrical equipment, bakelite products and in the preparation of paints, due to their high adhesive strength, high mechanical strength and excellent water resistance, heat resistance, chemical resistance and electrical insulation. However, since phenolic resin contains phenolic groups, the phenolic base is easy to oxidize into quinone to be reddish brown, and the color is darker after heat curing, for example, when the phenolic resin is used for producing decorative paper impregnation or thermosetting resin impregnation paper high-pressure laminated board (HPL), the original color and the printed pattern of the decorative material can be seriously affected, and the application of the decorative paper and the HPL in light clean occasions is not favored, so that the application of the phenolic resin is greatly limited. Thus, the preparation of light colored phenolic resins has been a focus of research.
At present, phenolic resin is subjected to light-color modification, for example, CN103819462A describes that melamine and urea are added in the preparation of the phenolic resin to modify the phenolic resin, so that the phenolic resin is light-colored to a certain extent, but the phenolic resin is brittle due to the addition of the melamine, and the water-soluble multiple of the phenolic resin is reduced due to the urea. CN101067016a describes the preparation of light colored phenolic resins by catalysis with divalent metal ions, but the phenolic resins prepared are more severely delaminated after a period of time. There are also some modification means with additional decolorizing agents, the main decolorizing additives are: malonyl thiourea, diphenyl thiourea, alpha-thiothiazolidine, alpha-mercaptobenzimidazole, thioglycollic acid and the like. The additive has two main functions, namely, the additive acts with the phenolic group to shield or prevent the phenolic group from being oxidized into quinone; secondly, the catalyst plays a role of a reducing agent to inhibit oxidation. However, the additive is added to have precipitation phenomenon in the long-term use process, and finally has problems in lasting effect, and even the mechanical property of the material can be influenced, so that the service life is influenced.
In view of the above, providing a phenolic resin with decolorizing durability is a technical problem to be solved.
Disclosure of Invention
The invention aims to solve the technical problems that: in order to solve the problem of poor decolorization durability of phenolic resin in the prior art, the invention provides a preparation method of environment-friendly modified light-color phenolic resin, functional monomers containing thiourea structures and epoxy groups are introduced in the preparation process, the thiourea structures and the epoxy groups in the molecular structures can act with phenol groups to shield phenol group oxidation, thereby being beneficial to improving the decolorization durability and solving the problem of poor decolorization durability of the phenolic resin in the prior art.
The technical scheme adopted for solving the technical problems is as follows:
the preparation method of the environment-friendly modified light-color phenolic resin comprises the following steps:
mixing a functional monomer with phenol, formaldehyde solution and ammonia water, heating to 80-90 ℃, reacting for 1-2 hours, heating to 85-95 ℃, decompressing and removing water and ammonia water under 0.03-0.04MPa, and reacting for 2-4 hours to obtain the environment-friendly modified light-color phenolic resin;
the molecular structure of the functional monomer contains a thiourea structure and an epoxy structure.
Optionally, the structure of the functional monomer is shown as the following formula:
optionally, the functional monomer is prepared according to the following method:
s1: adding p-hydroxybenzaldehyde and sodium hydroxide aqueous solution A into a three-neck flask under the protection of inert gas, stirring for 15-20min at 65-75 ℃, adding epichlorohydrin, preserving heat for 1.5-3h, cooling to room temperature, filtering, distilling under reduced pressure, and vacuum drying at 60 ℃ for 6h to obtain an intermediate product I;
s2: dissolving the intermediate product I, 5-amino-1, 3-dihydro-benzimidazole-2-thioketone in toluene, adjusting the pH value to 4-5, and then heating and refluxing; cooling to room temperature after the reaction is finished to generate sediment, filtering, taking the sediment, distilling the filtrate under reduced pressure to obtain insoluble substances, combining the insoluble substances with the sediment, and flushing the mixture with deionized water to obtain an intermediate product II;
s3: adding the intermediate product II and the sodium hydroxide aqueous solution B into a three-neck flask, heating to 75-85 ℃ for reaction for 1.5-3h, filtering, adding methylene dichloride for extraction, separating liquid, taking an organic phase, distilling under reduced pressure, and vacuum drying at 60 ℃ for 6h to obtain the functional monomer.
Alternatively, the aqueous sodium hydroxide solution a in step S1 and the aqueous sodium hydroxide solution B in step S3 are both 60wt% aqueous sodium hydroxide solutions.
Optionally, the dosage ratio of the parahydroxybenzaldehyde, the sodium hydroxide aqueous solution A and the epichlorohydrin in the step S1 is 1mol:16.7g: (1.2-1.7) mol.
Alternatively, the intermediate I, 5-amino-1, 3-dihydrobenzimidazole-2-thione is used in an amount ratio of 1mol in step S2: (1.2-1.5) mol.
Alternatively, the ratio of the amount of intermediate II, aqueous sodium hydroxide solution B, methylene chloride used in step S3 is 1mol:66.7g:300mL.
Alternatively, the formaldehyde solution is a 37wt% aqueous formaldehyde solution.
Optionally, the dosage ratio of the functional monomer, the phenol, the formaldehyde solution and the ammonia water is (0.02-0.05) mol: (0.95-0.98) mol: (81.1-121.6) g: (0.15-0.30) mol.
Another object of the present invention is to provide an environmentally friendly modified light-colored phenolic resin prepared by the method for preparing an environmentally friendly modified light-colored phenolic resin as described above.
The beneficial effects of the invention are as follows:
according to the preparation method of the environment-friendly modified light-colored phenolic resin, the functional monomer with the thiourea structure and the epoxy structure is introduced into the molecular structure, and the thiourea structure and the epoxy structure in the functional monomer can act with the phenol group to prevent the phenol group from oxidizing into quinone, so that the preparation method provided by the invention has the effect of high-efficiency decolorization, and is beneficial to obtaining the light-colored phenolic resin; secondly, the light-colored phenolic resin is obtained by a chemical synthesis modification method through the functional monomer, which is helpful for improving the decolorization durability.
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 decolorization durability of phenolic resin in the prior art, the invention provides a preparation method of environment-friendly modified light-color phenolic resin, which comprises the following steps:
mixing a functional monomer with phenol, formaldehyde solution and ammonia water, heating to 80-90 ℃, reacting for 1-2 hours, heating to 85-95 ℃, decompressing and removing water and ammonia water under 0.03-0.04MPa, and reacting for 2-4 hours to obtain the environment-friendly modified light-color phenolic resin; wherein the molecular structure of the functional monomer contains both thiourea structure and epoxy structure.
According to the preparation method of the environment-friendly modified light-colored phenolic resin, the functional monomer with the thiourea structure and the epoxy structure is introduced into the molecular structure, and the thiourea structure and the epoxy structure in the functional monomer can act with the phenol group to prevent the phenol group from oxidizing into quinone, so that the preparation method provided by the invention has the effect of high-efficiency decolorization, and is beneficial to obtaining the light-colored phenolic resin; secondly, the light-colored phenolic resin is obtained by a chemical synthesis modification method through the functional monomer, which is helpful for improving the decolorization durability.
Specifically, the structure of the preferred functional monomer of the invention is shown in the following formula:
after the thiourea structure and the epoxy structure in the functional monomer react with the phenol group, the functional monomer has certain toughness due to the fact that the functional monomer has larger molecular weight and contains hetero atoms, so that the defect of high brittleness of phenolic resin materials is overcome, and the toughness of light-color phenolic resin is improved; in addition, as the functional monomer has larger side groups and larger steric hindrance, the brittleness of the light-colored phenolic resin can be further improved, and the toughness of the light-colored phenolic resin can be further improved.
The functional monomer is preferably prepared according to the following method:
s1: adding p-hydroxybenzaldehyde and sodium hydroxide aqueous solution A into a three-neck flask under the protection of inert gas, stirring for 15-20min at 65-75 ℃, adding epichlorohydrin, preserving heat for 1.5-3h, cooling to room temperature, filtering, distilling under reduced pressure, and vacuum drying at 60 ℃ for 6h to obtain an intermediate product I;
s2: dissolving intermediate product I, 5-amino-1, 3-dihydro-benzimidazole-2-thioketone in toluene, regulating pH value to 4-5, and heating and refluxing; cooling to room temperature after the reaction is finished to generate sediment, filtering, taking the sediment, distilling the filtrate under reduced pressure to obtain insoluble substances, combining the insoluble substances with the sediment, and flushing the mixture with deionized water to obtain an intermediate product II;
s3: adding the intermediate product II and the sodium hydroxide aqueous solution B into a three-neck flask, heating to 75-85 ℃ for reaction for 1.5-3h, filtering, adding dichloromethane for extraction, separating liquid, taking an organic phase, distilling under reduced pressure, and vacuum drying at 60 ℃ for 6h to obtain a target product III, namely a functional monomer.
The preparation flow of the functional monomer is shown as the following formula:
the functional monomer is prepared from the p-hydroxybenzaldehyde, the epichlorohydrin and the 5-amino-1, 3-dihydro-benzimidazole-2-thioketone, the molecular structure of the functional monomer contains thiourea structure, epoxy group structure and hetero atoms, the molecular weight of the functional monomer is larger, the functional monomer has larger side groups, and larger steric hindrance is present, so that the high-efficiency decolorization effect is ensured, the decolorization durability is improved, the toughness of the phenolic resin material is improved, the mechanical property of the phenolic resin material is improved, and the light-color phenolic resin with decolorization durability and toughness is obtained.
In the present invention, it is preferable that the aqueous sodium hydroxide solution A in the step S1 and the aqueous sodium hydroxide solution B in the step S3 are both 60wt% aqueous sodium hydroxide solutions.
In order to consider the reaction rate and conversion rate in the preparation process of the functional monomer, the dosage ratio of the parahydroxybenzaldehyde, the sodium hydroxide aqueous solution A and the epichlorohydrin in the step S1 is preferably 1mol:16.7g: (1.2-1.7) mol; preferably, the intermediate I, 5-amino-1, 3-dihydrobenzimidazole-2-thione is used in step S2 in an amount ratio of 1mol: (1.2-1.5) mol, it is further preferred that the intermediate I, 5-amino-1, 3-dihydrobenzimidazole-2-thione, toluene, deionized water in step S2 is used in an amount ratio of 1mol: (1.2-1.5) mol:1000mL:500mL; preferably, in step S3, the ratio of the amount of intermediate II, aqueous sodium hydroxide solution B, and methylene chloride is 1mol:66.7g:300mL.
The formaldehyde solution is preferably a 37wt% aqueous formaldehyde solution.
In order to consider the decoloring durability and mechanical properties of the environment-friendly modified light-colored phenolic resin, the invention prefers the dosage ratio of functional monomer, phenol, formaldehyde solution and ammonia water to be (0.02-0.05) mol: (0.95-0.98) mol: (81.1-121.6) g: (0.15-0.30) mol.
The preparation method of the environment-friendly modified light-colored phenolic resin provided by the invention has the advantages of simple synthetic route, easiness in operation, simple technological process, convenience and reliability; the prepared environment-friendly modified light-colored phenolic resin has excellent decoloring durability, overcomes the defects of darker color and darker color after heat curing of the existing phenolic resin, and improves the mechanical properties of phenolic resin materials, thereby being beneficial to expanding the application range of the phenolic resin.
Another object of the present invention is to provide an environmentally friendly modified light-colored phenolic resin prepared by the method for preparing an environmentally friendly modified light-colored phenolic resin as described above.
According to the environment-friendly modified light-colored phenolic resin, functional monomers with thiourea structures and epoxy group structures are introduced into the molecular structures in the preparation process, and firstly, the thiourea structures and the epoxy group structures in the functional monomers can act with phenol groups to prevent the phenol groups from oxidizing into quinone, so that the preparation method provided by the invention has the effect of high-efficiency decolorization, and is beneficial to obtaining the light-colored phenolic resin; secondly, the light-colored phenolic resin is obtained by a chemical synthesis modification method through the functional monomer, which is helpful for improving the decolorization durability.
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 environment-friendly modified light-color phenolic resin, which comprises the following steps:
mixing a functional monomer with phenol, 37wt% of formaldehyde aqueous solution and ammonia water, heating to 85 ℃, reacting for 2 hours, heating to 90 ℃, decompressing and dehydrating under 0.03MPa, reacting for 3 hours, diluting deionized water, and uniformly stirring to obtain the environment-friendly modified light-color phenolic resin with the solid content of 50%;
wherein the dosage ratio of the functional monomer, phenol, 37 weight percent formaldehyde aqueous solution and ammonia water is 0.04mol:0.96mol:113.5g:0.25mol.
The preparation method of the functional monomer comprises the following steps:
s1: in N 2 Under the protection condition, adding p-hydroxybenzaldehyde and 60wt% sodium hydroxide aqueous solution A into a three-neck flask, stirring for 20min at 70 ℃, adding epichlorohydrin, preserving heat for 3h, cooling to room temperature after the reaction is finished, filtering, distilling under reduced pressure, and drying in vacuum at 60 ℃ for 6h to obtain an intermediate product I;
the dosage ratio of the parahydroxybenzaldehyde, 60wt% of sodium hydroxide aqueous solution A and epichlorohydrin is 1mol:16.7g:1.2mol;
the infrared data are as follows: 3372cm -1 : -OH is present; 3020cm -1 、1500cm -1 、774cm -1 : the benzene ring exists; 1720cm -1 : aldehyde-c=o present; 734cm -1 : -C-Cl is present; 943cm -1 、829cm -1 : epoxy groups are absent.
S2: dissolving an intermediate product I and 5-amino-1, 3-dihydro-benzimidazole-2-thione in toluene, slowly dropwise adding glacial acetic acid to adjust the pH value to 5, heating and refluxing for 24 hours, and continuously heating and refluxing for 3 hours after the water diversion quality of a water separator is constant in the reaction process; cooling to room temperature after the reaction is finished to generate sediment, filtering, taking the sediment, distilling the filtrate under reduced pressure to obtain insoluble substances, combining the insoluble substances with the sediment, and flushing the mixture with deionized water to obtain an intermediate product II;
the dosage ratio of the intermediate product I, the 5-amino-1, 3-dihydro-benzimidazole-2-thioketone, toluene and deionized water is 1mol:1.4mol:1000mL:500mL;
the infrared data are as follows: 3372cm -1 : -OH is present; 3020cm -1 、1500cm -1 、774cm -1 : benzene ring is storedIn the process of; 1545cm -1 : -N-H (amide) present; 1653cm -1 : -c=n-present; 1097cm -1 : -c=s present; 734cm -1 : -C-Cl is present; 1720cm -1 : aldehyde-c=o disappeared.
S3: adding the intermediate product II and 60wt% sodium hydroxide aqueous solution B into a three-neck flask, heating to 80 ℃ for reaction for 2 hours, filtering after the reaction is finished, adding dichloromethane for extraction, separating liquid, taking an organic phase, distilling under reduced pressure, and vacuum drying at 60 ℃ for 6 hours to obtain a target product III, namely a functional monomer;
the ratio of the amount of intermediate II, 60wt% aqueous sodium hydroxide solution B and methylene chloride used was 1mol:66.7g:300mL;
the infrared data are as follows: 3372cm -1 : -OH vanishes; 3020cm -1 、1500cm -1 、774cm -1 : the benzene ring exists; 1545cm -1 : -N-H (amide) present; 1653cm -1 : -c=n-present; 1097cm -1 : -c=s present; 945cm -1 、830cm -1 : the epoxy group is present; 734cm -1 : the C-Cl disappeared.
The nuclear magnetic hydrogen spectrum data are as follows: 1 H NMR(400MHz，CDCl 3 delta ppm): 7.2-8.5 (7H, benzene ring); 13.04 (2H, -NH-); 6.72 (1H, -CH-); 4.66 (1H, -CH-); 4.15 (2H, -CH) 2 -)；2.75(2H，-CH 2 -)。
Example 2
The embodiment provides a preparation method of environment-friendly modified light-color phenolic resin, which comprises the following steps:
mixing a functional monomer with phenol, 37wt% of formaldehyde aqueous solution and ammonia water, heating to 80 ℃, reacting for 2 hours, heating to 85 ℃, decompressing and dehydrating under 0.04MPa, reacting for 2 hours, diluting deionized water, and uniformly stirring to obtain the environment-friendly modified light-color phenolic resin with the solid content of 50%;
the dosage ratio of the functional monomer, phenol, 37 weight percent formaldehyde aqueous solution and ammonia water is 0.02mol:0.98mol:121.6g:0.30mol.
The preparation method of the functional monomer comprises the following steps:
s1: in N 2 Under the protection condition, adding p-hydroxybenzaldehyde and 60wt% sodium hydroxide aqueous solution A into a three-neck flask, stirring for 20min at 65 ℃, adding epichlorohydrin, preserving heat for 1.5h, cooling to room temperature after the reaction is finished, filtering, distilling under reduced pressure, and drying in vacuum at 60 ℃ for 6h to obtain an intermediate product I;
the dosage ratio of the parahydroxybenzaldehyde, 60wt% of sodium hydroxide aqueous solution A and epichlorohydrin is 1mol:16.7g:1.7mol;
the infrared data are as follows: 3372cm -1 : -OH is present; 3020cm -1 、1500cm -1 、774cm -1 : the benzene ring exists; 1720cm -1 : aldehyde-c=o present; 734cm -1 : -C-Cl is present; 943cm -1 、829cm -1 : epoxy groups are absent.
S2: dissolving an intermediate product I and 5-amino-1, 3-dihydro-benzimidazole-2-thione in toluene, slowly dripping glacial acetic acid to adjust the pH value to 4, heating and refluxing for 28 hours, and continuously heating and refluxing for 3 hours after the water diversion quality of a water separator is constant in the reaction process; cooling to room temperature after the reaction is finished to generate sediment, filtering, taking the sediment, distilling the filtrate under reduced pressure to obtain insoluble substances, combining the insoluble substances with the sediment, and flushing the mixture with deionized water to obtain an intermediate product II;
the dosage ratio of the intermediate product I, the 5-amino-1, 3-dihydro-benzimidazole-2-thioketone, toluene and deionized water is 1mol:1.2mol:1000mL:500mL;
the infrared data are as follows: 3372cm -1 : -OH is present; 3020cm -1 、1500cm -1 、774cm -1 : the benzene ring exists; 1545cm -1 : -N-H (amide) present; 1653cm -1 : -c=n-present; 1097cm -1 : -c=s present; 734cm -1 : -C-Cl is present; 1720cm -1 : aldehyde-c=o disappeared.
S3: adding the intermediate product II and 60wt% sodium hydroxide aqueous solution B into a three-neck flask, heating to 75 ℃ for reaction for 3 hours, filtering after the reaction is finished, adding dichloromethane for extraction, separating liquid, taking an organic phase, distilling under reduced pressure, and vacuum drying at 60 ℃ for 6 hours to obtain a target product III, namely a functional monomer;
the dosage ratio of the intermediate product II, the 60wt% sodium hydroxide aqueous solution B and the methylene dichloride is as follows: 1mol:66.7g:300mL;
the infrared data are as follows: 3372cm -1 : -OH vanishes; 3020cm -1 、1500cm -1 、774cm -1 : the benzene ring exists; 1545cm -1 : -N-H (amide) present; 1653cm -1 : -c=n-present; 1097cm -1 : -c=s present; 945cm -1 、830cm -1 : the epoxy group is present; 734cm -1 : the C-Cl disappeared.
The nuclear magnetic hydrogen spectrum data are as follows: 1 H NMR(400MHz，CDCl 3 delta ppm): 7.2-8.5 (7H, benzene ring); 13.04 (2H, -NH-); 6.72 (1H, -CH-); 4.66 (1H, -CH-); 4.15 (2H, -CH) 2 -)；2.75(2H，-CH 2 -)。
Example 3
The embodiment provides a preparation method of environment-friendly modified light-color phenolic resin, which comprises the following steps:
mixing a functional monomer with phenol, 37wt% of formaldehyde aqueous solution and ammonia water, heating to 90 ℃, reacting for 1h, heating to 95 ℃, decompressing and dehydrating under 0.04MPa, reacting for 4h, diluting deionized water, and uniformly stirring to obtain the environment-friendly modified light-color phenolic resin with the solid content of 50%;
the dosage ratio of the functional monomer, phenol, 37wt% formaldehyde aqueous solution and ammonia water is as follows: 0.05mol:0.95mol:81.1g:0.15mol.
The preparation method of the functional monomer comprises the following steps:
s1: in N 2 Under the protection condition, adding p-hydroxybenzaldehyde and 60wt% sodium hydroxide aqueous solution A into a three-neck flask, stirring for 15min at 75 ℃, adding epichlorohydrin, preserving heat for 2h, cooling to room temperature after the reaction is finished, filtering, distilling under reduced pressure, and drying in vacuum at 60 ℃ for 6h to obtain an intermediate product I;
the dosage ratio of the parahydroxybenzaldehyde, 60wt% of sodium hydroxide aqueous solution A and epichlorohydrin is 1mol:16.7g:1.4mol;
the infrared data are as follows: 3372cm -1 : -OH is present; 3020cm -1 、1500cm -1 、774cm -1 : the benzene ring exists; 1720cm -1 : aldehyde-c=o present; 734cm -1 : -C-Cl is present; 943cm -1 、829cm -1 : epoxy groups are absent.
S2: dissolving an intermediate product I and 5-amino-1, 3-dihydro-benzimidazole-2-thione in toluene, slowly dripping glacial acetic acid to adjust the pH value to 4, heating and refluxing for 20 hours, and continuously heating and refluxing for 3 hours after the water diversion quality of a water separator is constant in the reaction process; cooling to room temperature after the reaction is finished to generate sediment, filtering, taking the sediment, distilling the filtrate under reduced pressure to obtain insoluble substances, combining the insoluble substances with the sediment, and flushing the mixture with deionized water to obtain an intermediate product II;
the dosage ratio of the intermediate product I, the 5-amino-1, 3-dihydro-benzimidazole-2-thioketone, toluene and deionized water is 1mol:1.5mol:1000mL:500mL;
the infrared data are as follows: 3372cm -1 : -OH is present; 3020cm -1 、1500cm -1 、774cm -1 : the benzene ring exists; 1545cm -1 : -N-H (amide) present; 1653cm -1 : -c=n-present; 1097cm -1 : -c=s present; 734cm -1 : -C-Cl is present; 1720cm -1 : aldehyde-c=o disappeared.
S3: adding the intermediate product II and 60wt% sodium hydroxide aqueous solution B into a three-neck flask, heating to 85 ℃ for reaction for 1.5 hours, filtering after the reaction is finished, adding methylene dichloride for extraction, separating liquid, taking an organic phase, carrying out reduced pressure distillation, and carrying out vacuum drying at 60 ℃ for 6 hours to obtain a target product III, namely a functional monomer;
the ratio of the amount of intermediate II, 60wt% aqueous sodium hydroxide solution B and methylene chloride used was 1mol:66.7g:300mL;
the infrared data are as follows: 3372cm -1 : -OH vanishes; 3020cm -1 、1500cm -1 、774cm -1 : the benzene ring exists; 1545cm -1 : -N-H (amide) present; 1653cm -1 : -c=n-present; 1097cm -1 : -c=s present; 945cm -1 、830cm -1 : the epoxy group is present; 734cm -1 : the C-Cl disappeared.
The nuclear magnetic hydrogen spectrum data are as follows: 1 H NMR(400MHz，CDCl 3 delta ppm): 7.2-8.5 (7H, benzene ring); 13.04 (2H, -NH-); 6.72 (1H, -CH-); 4.66 (1H, -CH-); 4.15 (2H, -CH) 2 -)；2.75(2H，-CH 2 -)。
Example 4
The embodiment provides a preparation method of environment-friendly modified light-color phenolic resin, which comprises the following steps:
mixing a functional monomer with phenol, 37wt% of formaldehyde aqueous solution and ammonia water, heating to 90 ℃, reacting for 2 hours, heating to 95 ℃, decompressing and dehydrating under 0.03MPa, reacting for 3 hours, diluting deionized water, and uniformly stirring to obtain the environment-friendly modified light-color phenolic resin with the solid content of 50%;
the dosage ratio of the functional monomer, phenol, 37wt% formaldehyde aqueous solution and ammonia water is as follows: 0.04mol:0.96mol:121.6g:0.30mol.
The preparation method of the functional monomer comprises the following steps:
s1: in N 2 Under the protection condition, adding p-hydroxybenzaldehyde and 60wt% sodium hydroxide aqueous solution A into a three-neck flask, stirring for 15min at 70 ℃, adding epichlorohydrin, preserving heat for 1.5h, cooling to room temperature after the reaction is finished, filtering, distilling under reduced pressure, and drying in vacuum at 60 ℃ for 6h to obtain an intermediate product I;
the dosage ratio of the parahydroxybenzaldehyde, 60wt% of sodium hydroxide aqueous solution A and epichlorohydrin is 1mol:16.7g:1.5mol;
the infrared data are as follows: 3372cm -1 : -OH is present; 3020cm -1 、1500cm -1 、774cm -1 : the benzene ring exists; 1720cm -1 : aldehyde-c=o present; 734cm -1 : -C-Cl is present; 943cm -1 、829cm -1 : epoxy groups are absent.
S2: dissolving an intermediate product I and 5-amino-1, 3-dihydro-benzimidazole-2-thione in toluene, slowly dripping glacial acetic acid to adjust the pH value to 4, heating and refluxing for 26 hours, and continuously heating and refluxing for 3 hours after the water diversion quality of a water separator is constant in the reaction process; cooling to room temperature after the reaction is finished to generate sediment, filtering, taking the sediment, distilling the filtrate under reduced pressure to obtain insoluble substances, combining the insoluble substances with the sediment, and flushing the mixture with deionized water to obtain an intermediate product II;
the dosage ratio of the intermediate product I, the 5-amino-1, 3-dihydro-benzimidazole-2-thioketone, toluene and deionized water is 1mol:1.3mol:1000mL:500mL;
the infrared data are as follows: 3372cm -1 : -OH is present; 3020cm -1 、1500cm -1 、774cm -1 : the benzene ring exists; 1545cm -1 : -N-H (amide) present; 1653cm -1 : -c=n-present; 1097cm -1 : -c=s present; 734cm -1 : -C-Cl is present; 1720cm -1 : aldehyde-c=o disappeared.
S3: adding the intermediate product II and 60wt% sodium hydroxide aqueous solution B into a three-neck flask, heating to 80 ℃ for reaction for 1.5 hours, filtering after the reaction is finished, adding methylene dichloride for extraction, separating liquid, taking an organic phase, carrying out reduced pressure distillation, and carrying out vacuum drying at 60 ℃ for 6 hours to obtain a target product III, namely a functional monomer;
the ratio of the amount of intermediate II, 60wt% aqueous sodium hydroxide solution B and methylene chloride used was 1mol:66.7g:300mL;
the infrared data are as follows: 3372cm -1 : -OH vanishes; 3020cm -1 、1500cm -1 、774cm -1 : the benzene ring exists; 1545cm -1 : -N-H (amide) present; 1653cm -1 : -c=n-present; 1097cm -1 : -c=s present; 945cm -1 、830cm -1 : the epoxy group is present; 734cm -1 : the C-Cl disappeared.
The nuclear magnetic hydrogen spectrum data are as follows: 1 H NMR(400MHz，CDCl 3 delta ppm): 7.2-8.5 (7H, benzene ring); 13.04 (2H, -NH-); 6.72 (1H, -CH-); 4.66 (1H, -CH-); 4.15 (2H, -CH) 2 -)；2.75(2H，-CH 2 -)。
Example 5
The embodiment provides a preparation method of environment-friendly modified light-color phenolic resin, which comprises the following steps:
mixing a functional monomer with phenol, 37wt% of formaldehyde aqueous solution and ammonia water, heating to 85 ℃, reacting for 1h, heating to 90 ℃, decompressing and dehydrating under 0.03MPa, reacting for 3h, diluting deionized water, and uniformly stirring to obtain the environment-friendly modified light-color phenolic resin with the solid content of 50%;
the dosage ratio of the functional monomer, phenol, 37 weight percent formaldehyde aqueous solution and ammonia water is 0.04mol:0.96mol:81.1g:0.15mol.
The preparation method of the functional monomer comprises the following steps:
s1: in N 2 Under the protection condition, adding p-hydroxybenzaldehyde and 60wt% sodium hydroxide aqueous solution A into a three-neck flask, stirring for 20min at 75 ℃, adding epichlorohydrin, preserving heat for 3h, cooling to room temperature after the reaction is finished, filtering, distilling under reduced pressure, and drying in vacuum at 60 ℃ for 6h to obtain an intermediate product I;
the dosage ratio of the parahydroxybenzaldehyde, 60wt% of sodium hydroxide aqueous solution A and epichlorohydrin is 1mol:16.7g:1.2mol;
the infrared data are as follows: 3372cm -1 : -OH is present; 3020cm -1 、1500cm -1 、774cm -1 : the benzene ring exists; 1720cm -1 : aldehyde-c=o present; 734cm -1 : -C-Cl is present; 943cm -1 、829cm -1 : epoxy groups are absent.
S2: dissolving an intermediate product I and 5-amino-1, 3-dihydro-benzimidazole-2-thione in toluene, slowly dripping glacial acetic acid to adjust the pH value to 4, heating and refluxing for 24 hours, and continuously heating and refluxing for 3 hours after the water diversion quality of a water separator is constant in the reaction process; cooling to room temperature after the reaction is finished to generate sediment, filtering, taking the sediment, distilling the filtrate under reduced pressure to obtain insoluble substances, combining the insoluble substances with the sediment, and flushing the mixture with deionized water to obtain an intermediate product II;
the dosage ratio of the intermediate product I, the 5-amino-1, 3-dihydro-benzimidazole-2-thioketone, toluene and deionized water is 1mol:1.5mol:1000mL:500mL;
the infrared data are as follows: 3372cm -1 : -OH is present; 3020cm -1 、1500cm -1 、774cm -1 : the benzene ring exists; 1545cm -1 : -N-H (amide) present; 1653cm -1 : -c=n-present; 1097cm -1 : -c=s present; 734cm -1 : -C-Cl is present; 1720cm -1 : aldehyde group-C=o disappears.
S3: adding the intermediate product II and 60wt% sodium hydroxide aqueous solution B into a three-neck flask, heating to 75 ℃ for reaction for 2 hours, filtering after the reaction is finished, adding dichloromethane for extraction, separating liquid, taking an organic phase, distilling under reduced pressure, and vacuum drying at 60 ℃ for 6 hours to obtain a target product III, namely a functional monomer;
the ratio of the amount of intermediate II, 60wt% aqueous sodium hydroxide solution B and methylene chloride used was 1mol:66.7g:300mL;
the infrared data are as follows: 3372cm -1 : -OH vanishes; 3020cm -1 、1500cm -1 、774cm -1 : the benzene ring exists; 1545cm -1 : -N-H (amide) present; 1653cm -1 : -c=n-present; 1097cm -1 : -c=s present; 945cm -1 、830cm -1 : the epoxy group is present; 734cm -1 : the C-Cl disappeared.
The nuclear magnetic hydrogen spectrum data are as follows: 1 H NMR(400MHz，CDCl 3 delta ppm): 7.2-8.5 (7H, benzene ring); 13.04 (2H, -NH-); 6.72 (1H, -CH-); 4.66 (1H, -CH-); 4.15 (2H, -CH) 2 -)；2.75(2H，-CH 2 -)。
Example 6
The embodiment provides a preparation method of environment-friendly modified light-color phenolic resin, which comprises the following steps:
mixing a functional monomer with phenol, 37wt% of formaldehyde aqueous solution and ammonia water, heating to 85 ℃, reacting for 2 hours, heating to 95 ℃, decompressing and dehydrating under 0.03MPa, reacting for 3 hours, diluting deionized water, and uniformly stirring to obtain the environment-friendly modified light-color phenolic resin with the solid content of 50%;
the dosage ratio of the functional monomer, phenol, 37 weight percent formaldehyde aqueous solution and ammonia water is 0.03mol:0.97mol:113.5g:0.25mol.
The preparation method of the functional monomer comprises the following steps:
s1: in N 2 Under the protection condition, adding p-hydroxybenzaldehyde and 60wt% sodium hydroxide aqueous solution A into a three-neck flask, stirring for 15min at 65 ℃, adding epichlorohydrin, preserving heat for 2h, and reducing after the reaction is finishedFiltering, distilling under reduced pressure, and vacuum drying at 60deg.C for 6 hr to obtain intermediate I;
the dosage ratio of the parahydroxybenzaldehyde, 60wt% of sodium hydroxide aqueous solution A and epichlorohydrin is 1mol:16.7g:1.7mol;
the infrared data are as follows: 3372cm -1 : -OH is present; 3020cm -1 、1500cm -1 、774cm -1 : the benzene ring exists; 1720cm -1 : aldehyde-c=o present; 734cm -1 : -C-Cl is present; 943cm -1 、829cm -1 : epoxy groups are absent.
S2: dissolving an intermediate product I and 5-amino-1, 3-dihydro-benzimidazole-2-thione in toluene, slowly dripping glacial acetic acid to adjust the pH value to 5, heating and refluxing for 24 hours, and continuously heating and refluxing for 3 hours after the water diversion quality of a water separator is constant in the reaction process; cooling to room temperature after the reaction is finished to generate sediment, filtering, taking the sediment, distilling the filtrate under reduced pressure to obtain insoluble substances, combining the insoluble substances with the sediment, and flushing the mixture with deionized water to obtain an intermediate product II;
the dosage ratio of the intermediate product I, the 5-amino-1, 3-dihydro-benzimidazole-2-thioketone, toluene and deionized water is 1mol:1.2mol:1000mL:500mL;
the infrared data are as follows: 3372cm -1 : -OH is present; 3020cm -1 、1500cm -1 、774cm -1 : the benzene ring exists; 1545cm -1 : -N-H (amide) present; 1653cm -1 : -c=n-present; 1097cm -1 : -c=s present; 734cm -1 : -C-Cl is present; 1720cm -1 : aldehyde-c=o disappeared.
S3: adding the intermediate product II and 60wt% sodium hydroxide aqueous solution B into a three-neck flask, heating to 85 ℃ for reaction for 2 hours, filtering after the reaction is finished, adding dichloromethane for extraction, separating liquid, taking an organic phase, distilling under reduced pressure, and vacuum drying at 60 ℃ for 6 hours to obtain a target product III, namely a functional monomer;
the ratio of the amount of intermediate II, 60wt% aqueous sodium hydroxide solution B and methylene chloride used was 1mol:66.7g:300mL;
the infrared data are as follows: 3372cm -1 : -OH vanishes; 3020cm -1 、1500cm -1 、774cm -1 : the benzene ring exists; 1545cm -1 : -N-H (amide) present; 1653cm -1 : -c=n-present; 1097cm -1 : -c=s present; 945cm -1 、830cm -1 : the epoxy group is present; 734cm -1 : the C-Cl disappeared.
The nuclear magnetic hydrogen spectrum data are as follows: 1 H NMR(400MHz，CDCl 3 delta ppm): 7.2-8.5 (7H, benzene ring); 13.04 (2H, -NH-); 6.72 (1H, -CH-); 4.66 (1H, -CH-); 4.15 (2H, -CH) 2 -)；2.75(2H，-CH 2 -)。
The following comparative examples are all compared to example 1:
comparative example 1
The comparative example provides a method for preparing phenolic resin, comprising the following steps:
mixing phenol, 37wt% of formaldehyde aqueous solution and ammonia water, heating to 85 ℃, reacting for 2 hours, heating to 90 ℃, decompressing and dehydrating under 0.03MPa, and reacting for 3 hours to obtain environment-friendly modified light-color phenolic resin;
phenol, 37wt% aqueous formaldehyde solution, ammonia water in an amount ratio of 1.0mol:113.5g:0.25mol.
Comparative example 2
The comparative example provides a method for preparing phenolic resin, comprising the following steps:
mixing a functional monomer with phenol, 37wt% formaldehyde aqueous solution and ammonia water, heating to 85 ℃, reacting for 2 hours, heating to 90 ℃, decompressing and dehydrating under 0.03MPa, and reacting for 3 hours to obtain the environment-friendly modified light-color phenolic resin;
the dosage ratio of the functional monomer, phenol, 37 weight percent formaldehyde aqueous solution and ammonia water is 0.04mol:0.96mol:113.5g:0.25mol.
The preparation method of the functional monomer comprises the following steps:
s1: in N 2 Under the protection condition, adding phenol and 60wt% sodium hydroxide aqueous solution A into a three-neck flask, stirring for 20min at 70 ℃, adding epichlorohydrin, preserving heat for 3h, cooling to room temperature after the reaction is finished, filtering, distilling under reduced pressure, and vacuum drying at 60 ℃ for 6h to obtainIntermediate I;
phenol, 60wt% aqueous sodium hydroxide solution A, epichlorohydrin in an amount ratio of 1mol:16.7g:1.2mol;
the infrared data are as follows: 3372cm -1 : -OH is present; 3020cm -1 、1500cm -1 、774cm -1 : the benzene ring exists; 734cm -1 : -C-Cl is present; 943cm -1 、829cm -1 : epoxy groups are absent.
S2: adding the intermediate product I and 60wt% sodium hydroxide aqueous solution B into a three-neck flask, heating to 80 ℃ for reaction for 2 hours, filtering after the reaction is finished, adding dichloromethane for extraction, separating liquid, taking an organic phase, distilling under reduced pressure, and vacuum drying at 60 ℃ for 6 hours to obtain a target product II, namely a functional monomer;
the ratio of the amount of intermediate I, 60wt% aqueous sodium hydroxide solution B and methylene chloride is 1mol:66.7g:300mL;
the infrared data are as follows: 3372cm -1 : -OH vanishes; 3020cm -1 、1500cm -1 、774cm -1 : the benzene ring exists; 945cm -1 、830cm -1 : the epoxy group is present; 734cm -1 : the C-Cl disappeared.
Comparative example 3
The comparative example provides a method for preparing phenolic resin, comprising the following steps:
mixing a functional monomer with phenol, 37wt% formaldehyde aqueous solution and ammonia water, heating to 85 ℃, reacting for 2 hours, heating to 90 ℃, decompressing and dehydrating under 0.03MPa, and reacting for 3 hours to obtain the environment-friendly modified light-color phenolic resin;
the dosage ratio of the functional monomer, phenol, 37 weight percent formaldehyde aqueous solution and ammonia water is 0.04mol:0.96mol:113.5g:0.25mol.
The preparation method of the functional monomer comprises the following steps:
dissolving p-hydroxybenzaldehyde and 5-amino-1, 3-dihydro-benzimidazole-2-thione in toluene, slowly dripping glacial acetic acid to adjust pH value to 5, heating and refluxing for 24 hours, and continuously heating and refluxing for 3 hours after the water diversion quality of a water separator is constant in the reaction process; cooling to room temperature after the reaction is finished, generating a precipitate, filtering, taking the precipitate, distilling the filtrate under reduced pressure to obtain an insoluble substance, combining the insoluble substance with the precipitate, and washing the mixture with deionized water to obtain a target product;
the dosage ratio of the p-hydroxybenzaldehyde, the 5-amino-1, 3-dihydro-benzimidazole-2-thioketone, toluene and deionized water is 1mol:1.4mol:1000mL:500mL;
the infrared data are as follows: 3404cm -1 : -OH is present; 3020cm -1 、1500cm -1 、774cm -1 : the benzene ring exists; 1545cm -1 : -N-H (amide) present; 1653cm -1 : -c=n-present; 1097cm -1 : -c=s present; 1720cm -1 : aldehyde-c=o disappeared.
Comparative example 4
The comparative example provides a method for preparing phenolic resin, comprising the following steps:
mixing phenol, 37wt% of formaldehyde aqueous solution and ammonia water, heating to 85 ℃, reacting for 2 hours, heating to 90 ℃, decompressing and dehydrating under 0.03MPa, reacting for 3 hours, cooling to room temperature after the reaction is finished, adding functional monomers, and uniformly stirring to obtain the environment-friendly modified light-color phenolic resin;
the dosage ratio of the functional monomer, phenol, 37 weight percent formaldehyde aqueous solution and ammonia water is 0.04mol:0.96mol:113.5g:0.25mol.
The preparation method of the functional monomer is the same as in example 1.
The phenolic resins obtained in examples 1 to 6 and comparative examples 1 to 4 were prepared as adhesives, respectively, by the following methods:
dispersing 100 parts by weight of phenolic resin at the room temperature under the condition of 100r/min, adding 0.2 part by weight of BYK-a525 defoamer and proper amount of water, uniformly mixing, adjusting the stirring speed to 300r/min, stirring for 10min, and standing to obtain the phenolic resin adhesive with the solid content of 35%.
The phenolic resin adhesive is adopted to carry out dipping and drying treatment on the decorative base paper, so as to obtain dipping decorative paper; the plurality of impregnated decorative paper layers are pressed to produce a thermosetting resin impregnated paper high pressure decorative laminate (HPL), and the relevant physical properties are tested according to the national standard GB/T7911-2013 thermosetting resin impregnated paper high pressure decorative laminate (HPL).
The test method comprises the following steps:
appearance, solids content, free phenol content: the test was carried out as described in GB/T14732-2017.
Iron cobalt colorimetric/no: the tests were carried out according to the method described in GB/T1722-92, on day 1 and 30 respectively, under open storage conditions at room temperature.
Color, crack resistance, ball impact resistance: the test was carried out as described in GB/T7911-2013.
The test results are shown in Table 1:
TABLE 1
As shown in the data in the table, compared with the phenolic resin modified by the functional monomer not added in comparative example 1, the environment-friendly modified light-color phenolic resin prepared in each embodiment of the invention has the characteristics of greatly improving the color, improving the decoloring durability, further improving the mechanical strength, and proving that the functional monomer provided by the invention has excellent decoloring performance, decoloring durability and improving the toughness of the phenolic resin.
The technical solution provided in comparative example 2, although having improved mechanical properties as compared with the solution in comparative example 1 in which the phenolic resin was not modified, had no obvious effect of improving discoloration and the durability of the discoloration.
The technical scheme provided in comparative example 3, although having improved discoloration performance and discoloration durability compared with the scheme in comparative example 1 in which the phenolic resin was not modified, had poor discoloration performance, discoloration durability and mechanical properties compared with example 1.
Comparing comparative example 4 with the protocol of example 1, it can be seen that the long-term efficacy of the chemical modification is significantly better than the way in which the physical blend is made.
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 (10)
1. The preparation method of the environment-friendly modified light-colored phenolic resin is characterized by comprising the following steps of:
mixing a functional monomer with phenol, formaldehyde solution and ammonia water, heating to 80-90 ℃, reacting for 1-2 hours, heating to 85-95 ℃, decompressing and removing water and ammonia water under 0.03-0.04MPa, and reacting for 2-4 hours to obtain the environment-friendly modified light-color phenolic resin;
the molecular structure of the functional monomer contains a thiourea structure and an epoxy structure.
2. The method for preparing the environment-friendly modified light-colored phenolic resin according to claim 1, wherein the structure of the functional monomer is shown as the following formula:
3. the method for preparing the environment-friendly modified light-colored phenolic resin according to claim 2, wherein the functional monomer is prepared according to the following method:
s1: adding p-hydroxybenzaldehyde and sodium hydroxide aqueous solution A into a three-neck flask under the protection of inert gas, stirring for 15-20min at 65-75 ℃, adding epichlorohydrin, preserving heat for 1.5-3h, cooling to room temperature, filtering, distilling under reduced pressure, and vacuum drying at 60 ℃ for 6h to obtain an intermediate product I;
s2: dissolving the intermediate product I, 5-amino-1, 3-dihydro-benzimidazole-2-thioketone in toluene, adjusting the pH value to 4-5, and then heating and refluxing; cooling to room temperature after the reaction is finished to generate sediment, filtering, taking the sediment, distilling the filtrate under reduced pressure to obtain insoluble substances, combining the insoluble substances with the sediment, and flushing the mixture with deionized water to obtain an intermediate product II;
s3: adding the intermediate product II and the sodium hydroxide aqueous solution B into a three-neck flask, heating to 75-85 ℃ for reaction for 1.5-3h, filtering, adding methylene dichloride for extraction, separating liquid, taking an organic phase, distilling under reduced pressure, and vacuum drying at 60 ℃ for 6h to obtain the functional monomer.
4. The process for preparing an environmentally friendly modified light-colored phenolic resin according to claim 3, wherein the aqueous sodium hydroxide solution A in the step S1 and the aqueous sodium hydroxide solution B in the step S3 are 60wt% aqueous sodium hydroxide solutions.
5. The method for preparing the environment-friendly modified light-colored phenolic resin, as claimed in claim 4, wherein the dosage ratio of the parahydroxybenzaldehyde, the sodium hydroxide aqueous solution A and the epichlorohydrin in the step S1 is 1mol:16.7g: (1.2-1.7) mol.
6. The method for preparing the environment-friendly modified light-colored phenolic resin, as claimed in claim 4, wherein the dosage ratio of the intermediate product I, 5-amino-1, 3-dihydrobenzimidazole-2-thione in the step S2 is 1mol: (1.2-1.5) mol.
7. The method for preparing the environment-friendly modified light-colored phenolic resin, as claimed in claim 4, wherein the dosage ratio of the intermediate product II, the sodium hydroxide aqueous solution B and the methylene dichloride in the step S3 is 1mol:66.7g:300mL.
8. The method of preparing an environmentally friendly modified light-colored phenolic resin of any one of claims 1 to 7, wherein the formaldehyde solution is a 37% by weight aqueous formaldehyde solution.
9. The method for preparing the environment-friendly modified light-colored phenolic resin according to claim 8, wherein the dosage ratio of the functional monomer to the phenol to the formaldehyde solution to the ammonia water is (0.02-0.05) mol: (0.95-0.98) mol: (81.1-121.6) g: (0.15-0.30) mol.
10. An environmentally friendly modified light-colored phenolic resin prepared by the process of any one of claims 1 to 9.
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| US5679766A (en) * | 1993-12-07 | 1997-10-21 | Shipley Company, L.L.C. | Purification process of novolar resins using acid treated chelating cation exchange resin |
| US20180244824A1 (en) * | 2017-02-27 | 2018-08-30 | Avalon Industries Ag | Method for producing thermosetting phenolic resins and phenolic resins obtainable by the method |
| CN109073976A (en) * | 2016-04-28 | 2018-12-21 | 日产化学株式会社 | It is used to form the composition for the resist lower membrane that film density improves |
| CN111269371A (en) * | 2020-04-09 | 2020-06-12 | 山东阳谷华泰化工股份有限公司 | Preparation method of light-colored alkylphenol phenolic resin |
| US20210047457A1 (en) * | 2018-01-22 | 2021-02-18 | Mitsubishi Gas Chemical Company, Inc. | Compound, resin, composition and pattern formation method |
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|---|---|---|---|---|
| US5679766A (en) * | 1993-12-07 | 1997-10-21 | Shipley Company, L.L.C. | Purification process of novolar resins using acid treated chelating cation exchange resin |
| CN109073976A (en) * | 2016-04-28 | 2018-12-21 | 日产化学株式会社 | It is used to form the composition for the resist lower membrane that film density improves |
| US20180244824A1 (en) * | 2017-02-27 | 2018-08-30 | Avalon Industries Ag | Method for producing thermosetting phenolic resins and phenolic resins obtainable by the method |
| US20210047457A1 (en) * | 2018-01-22 | 2021-02-18 | Mitsubishi Gas Chemical Company, Inc. | Compound, resin, composition and pattern formation method |
| CN111269371A (en) * | 2020-04-09 | 2020-06-12 | 山东阳谷华泰化工股份有限公司 | Preparation method of light-colored alkylphenol phenolic resin |
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