CN112661978A - Emulsifiable low-aldehyde environment-friendly water-based phenolic resin and preparation method and application thereof - Google Patents
Emulsifiable low-aldehyde environment-friendly water-based phenolic resin and preparation method and application thereof Download PDFInfo
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- CN112661978A CN112661978A CN202011587398.5A CN202011587398A CN112661978A CN 112661978 A CN112661978 A CN 112661978A CN 202011587398 A CN202011587398 A CN 202011587398A CN 112661978 A CN112661978 A CN 112661978A
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Abstract
The invention discloses an emulsifiable low-aldehyde environment-friendly water-based phenolic resin and a preparation method and application thereof, wherein the emulsified low-aldehyde environment-friendly water-based phenolic resin comprises the following components: 50-80 parts of phenolic resin, 1-10 parts of emulsion stabilizer and 20-50 parts of water. The phenolic resin prepared by emulsifying the phenolic resin by the specific emulsion stabilizer has low content of free components and low release amount of volatile organic compounds, and meanwhile, the phenolic resin has good water solubility, can be directly diluted by water in the using process, does not need to be added with an organic solvent, thereby reducing the use of the organic solvent, improving the operating environment, being beneficial to the health of operators, reducing the environmental pollution and having better toughness.
Description
Technical Field
The invention relates to the technical field of phenolic resin, in particular to emulsifiable low-formaldehyde environment-friendly water-based phenolic resin and a preparation method and application thereof.
Background
The water-borne phenolic resin is a synthetic resin with wide application, and is mainly polymerized by formaldehyde and phenol under the action of a catalyst. In the traditional phenolic resin manufacturing process, more free components such as formaldehyde and the like are left, because when the reaction is carried out to a certain degree, the molecular chain is too long, and the molecular weight is too large, so that the solution phase splitting is caused, and the stability and the usability of the resin solution are influenced. Therefore, to meet the usefulness of the resin, the reaction must be controlled to a certain extent, which results in the final product having a large amount of free components left.
In addition, in the preparation process of the traditional phenolic resin, when the molecular weight is too large, the water solubility is not high, so that the solution phase separation is caused, a large amount of organic solvent is required to be used at the moment, otherwise, a large amount of precipitation and precipitation are caused due to too low water solubility of the resin, and the resin cannot be normally used. The use of a large amount of organic solvent causes pollution to the environment and harms the health of operators.
Disclosure of Invention
According to the invention, on the premise of not changing the formula of the resin liquid and not influencing the mechanical property of the resin liquid after solidification, the water-soluble property of the resin liquid is maintained by adding the emulsion stabilizer, so that the reaction time of the preparation process of the resin liquid can be prolonged, and the content of free components in a finished product of the resin liquid is effectively reduced, thereby improving the environmental protection property of the resin, reducing VOC (volatile organic compound) emission and improving the operation friendliness. Meanwhile, good water solubility is maintained, and the mechanical property is improved.
The invention provides an emulsifiable low-aldehyde environment-friendly water-based phenolic resin, which has good water solubility, can be directly diluted by water in the using process and does not need to be added with an organic solvent.
The invention also aims to provide a preparation method of the emulsifiable low-aldehyde environment-friendly water-based phenolic resin.
The invention is realized by the following technical scheme:
an emulsifiable low-aldehyde environment-friendly water-based phenolic resin comprises the following components in parts by weight:
50-80 parts of phenolic resin
1-10 parts of emulsion stabilizer
20-50 parts of water.
The phenolic resin can be obtained by condensation polymerization of formaldehyde and phenol according to a conventional method, and can also be modified phenolic resin obtained by modification of bisphenol A, melamine, urea or alkylphenol. It can be obtained from commercial products or made by self.
Preferably, the emulsion stabilizer is one or a mixture of more of amino acid, vegetable protein, gelatin, bone glue or animal protein. The vegetable protein may be soybean protein isolate, etc., and the animal protein may be blood protein, casein, etc.
The emulsion stabilizer selected by the invention has both hydrophilicity and lipophilicity, one lipophilic end is connected with phenolic resin molecules, and the other hydrophilic end is connected with water molecules, so that the hydrophilicity and the stability of the phenolic resin in water are improved, the phenolic resin can be better combined with a base material, and the toughness of the cured resin can be improved.
The invention also provides a preparation method of the emulsifiable low-aldehyde environment-friendly water-based phenolic resin, which comprises the following steps:
taking phenol and formaldehyde as raw materials, adding an alkaline catalyst into the phenol, heating to 40-90 ℃, adding the formaldehyde, performing constant-temperature polycondensation until the water solubility of the reaction mixture is 1-6, adding an emulsion stabilizer, reacting for 1-3 hours, and cooling to below 40 ℃ to obtain the emulsifiable low-formaldehyde environment-friendly water-based phenolic resin. Wherein the molar ratio of the formaldehyde to the phenol is 1.2-2.0.
Preferably, the alkaline catalyst is one or a mixture of sodium hydroxide, potassium hydroxide or barium hydroxide.
The research of the invention finds that when the reaction is carried out to a certain degree in the phenolic resin manufacturing process, the molecular chain is too long, and the molecular weight is too large, so that the precipitation can be caused, the reaction can not be carried out continuously, and the free components are more.
The invention also provides the application of the emulsifiable low-formaldehyde environment-friendly water-based phenolic resin in the fields of scouring pad, base coating of abrasive cloth, cloth base treatment of abrasive cloth and filter paper impregnation.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the phenolic resin is added with the specific emulsion stabilizer, so that the prepared emulsifiable low-aldehyde environment-friendly water-based phenolic resin has good water solubility, can be directly diluted with water in the using process, and does not need to add an organic solvent, thereby reducing the use of the organic solvent, improving the operating environment, being beneficial to the health of operators and reducing the environmental pollution.
The emulsion stabilizer can be added in the reaction process of the phenolic resin, and can also be directly blended with the phenolic resin after the reaction. If the emulsifier is added in the reaction process, the emulsion stabilizer can improve the water solubility of the resin macromolecules, so that the reaction time can be prolonged, and free components can be reduced, thereby reducing VOC (volatile organic compounds) emission and being more environment-friendly.
The emulsifiable low-formaldehyde environment-friendly water-based phenolic resin prepared by the invention has better toughness, and the grinding performance of the grinding material prepared by the emulsified low-formaldehyde environment-friendly water-based phenolic resin can be obviously improved.
Detailed Description
The present invention is further illustrated by the following specific examples, which are, however, not intended to limit the scope of the invention.
The raw materials adopted by the invention can be obtained commercially.
Example 1:
an emulsifiable low-aldehyde environment-friendly water-based phenolic resin comprises the following components in parts by weight: 65 parts of phenolic resin, 3 parts of isolated soy protein and 32 parts of water.
The preparation process comprises the following steps:
taking phenol and formaldehyde as raw materials, adding sodium hydroxide into the phenol, heating to 80 ℃, adding the formaldehyde, performing constant-temperature polycondensation until the water solubility of a reaction mixture is 2, adding isolated soy protein, reacting for 2 hours, and cooling to below 40 ℃ to obtain the emulsifiable low-formaldehyde environment-friendly water-based phenolic resin. Wherein the molar ratio of formaldehyde to phenol is 1.8.
Example 2:
an emulsifiable low-aldehyde environment-friendly water-based phenolic resin comprises the following components in parts by weight: 70 parts of phenolic resin, 4 parts of gelatin and 26 parts of water.
The preparation process comprises the following steps:
taking phenol and formaldehyde as raw materials, adding sodium hydroxide into the phenol, heating to 90 ℃, adding the formaldehyde, performing constant-temperature polycondensation until the water solubility of a reaction mixture is 3, adding gelatin, reacting for 2 hours, and cooling to below 40 ℃ to obtain the emulsifiable low-formaldehyde environment-friendly water-based phenolic resin. Wherein the molar ratio of formaldehyde to phenol is 1.5.
Example 3:
an emulsifiable low-aldehyde environment-friendly water-based phenolic resin comprises the following components in parts by weight: 75 parts of phenolic resin, 5 parts of bone glue and 20 parts of water.
The preparation process comprises the following steps:
taking phenol and formaldehyde as raw materials, adding potassium hydroxide into the phenol, heating to 75 ℃, adding the formaldehyde, performing constant-temperature polycondensation until the water solubility of the reaction mixture is 1, adding bone glue, reacting for 2 hours, and cooling to below 40 ℃ to obtain the emulsifiable low-formaldehyde environment-friendly water-based phenolic resin. Wherein the molar ratio of formaldehyde to phenol is 1.6.
Example 4:
an emulsifiable low-aldehyde environment-friendly water-based phenolic resin comprises the following components in parts by weight: 55 parts of phenolic resin, 2 parts of casein and 43 parts of water.
The preparation process comprises the following steps:
uniformly mixing the phenolic resin, casein and water to obtain the emulsifiable low-aldehyde environment-friendly water-based phenolic resin.
Example 5:
an emulsifiable low-aldehyde environment-friendly water-based phenolic resin comprises the following components in parts by weight: 65 parts of modified phenolic resin, 5 parts of amino acid and 30 parts of water.
The preparation process comprises the following steps:
taking phenol, bisphenol A and formaldehyde as raw materials, adding water into bisphenol A, heating to 90 ℃ for dissolution, then adding phenol and potassium hydroxide, cooling to 75 ℃, adding formaldehyde, performing constant-temperature polycondensation until the water solubility of a reaction mixture is 1, adding amino acid, reacting for 2 hours, and cooling to below 40 ℃ to obtain the emulsifiable low-formaldehyde environment-friendly water-based phenolic resin. Wherein the molar ratio of formaldehyde to phenol is 1.4.
The phenolic resin prepared in the examples 1-5 and the existing phenolic resin are cured or prepared into a grinding wheel product, the performance of the grinding wheel product is tested, and the test results are shown in table 1.
TABLE 1 Performance results
The results in table 1 show that, compared with the conventional phenolic resin, the emulsified low-formaldehyde environment-friendly water-based phenolic resin prepared by emulsifying the phenolic resin with the specific emulsion stabilizer can obviously reduce the emission of VOC after being cured, is more environment-friendly and has better toughness. The grinding performance of the grinding wheel product prepared by the grinding wheel is obviously improved.
Application example 1:
preparing a sizing material: adding the emulsifiable low-formaldehyde environment-friendly water-based phenolic resin prepared in the embodiment 1, silicon carbide serving as an abrasive, a defoaming agent, a leveling agent and silane into the water-based color paste, calcium carbonate, a toughening agent and the ABS emulsion, uniformly mixing, and adding water to adjust to proper viscosity for later use;
gum dipping: dipping the prepared scouring pad gray cloth in the prepared slurry, and extruding the redundant sizing material through a rubber roller;
spraying glue: atomizing the sizing material on the front side and the back side of the product through high pressure, and spraying the sizing material on the two sides of the scouring pad;
and (3) drying: drying and curing the product for 7-15min at 150 ℃ in a curing furnace;
cutting a finished product: the finished product is cut and processed into various products with different properties.
The emulsified low-aldehyde environment-friendly water-based phenolic resin prepared by the invention has good compatibility and good miscibility with various auxiliary materials; the method is suitable for the high-pressure atomization process, does not need to use a solvent, reduces the possibility of flammability and explosiveness, and improves the environmental protection performance; substantially achieve grinding performance consistent with current solvent based products.
Claims (8)
1. An emulsifiable low-aldehyde environment-friendly water-based phenolic resin is characterized by comprising the following components in parts by weight:
50-80 parts of phenolic resin
1-10 parts of emulsion stabilizer
20-50 parts of water.
2. The emulsifiable low-aldehyde environmentally friendly water-based phenolic resin according to claim 1, wherein: the phenolic resin is modified by bisphenol A, melamine, urea or alkyl phenol.
3. The emulsifiable low-aldehyde environmentally friendly water-based phenolic resin according to claim 1, wherein: the emulsion stabilizer is one or a mixture of more of amino acid, vegetable protein, gelatin, bone glue or animal protein.
4. The preparation method of the emulsifiable low-aldehyde environment-friendly water-based phenolic resin is characterized by comprising the following steps:
taking phenol and formaldehyde as raw materials, adding an alkaline catalyst into the phenol, heating to 40-90 ℃, adding the formaldehyde, performing constant-temperature polycondensation until the water solubility of the reaction mixture is 1-6, adding an emulsion stabilizer, reacting for 1-3 hours, and cooling to below 40 ℃ to obtain the emulsifiable low-formaldehyde environment-friendly water-based phenolic resin.
5. The method for preparing the emulsifiable low-aldehyde environment-friendly water-based phenolic resin according to claim 4, wherein the method comprises the following steps: the molar ratio of the formaldehyde to the phenol is 1.2-2.0.
6. The method for preparing the emulsifiable low-aldehyde environment-friendly water-based phenolic resin according to claim 4, wherein the method comprises the following steps: the alkaline catalyst is one or a mixture of sodium hydroxide, potassium hydroxide or barium hydroxide.
7. The preparation method of the emulsifiable low-aldehyde environment-friendly water-based phenolic resin is characterized by comprising the following steps:
according to the weight portion, 50-80 portions of phenolic resin, 1-10 portions of emulsion stabilizer and 20-50 portions of water are uniformly mixed, and the material is obtained.
8. Use of the emulsifiable low-aldehyde eco-friendly water-based phenolic resin as claimed in any one of claims 1 to 3 in the field of scouring pads, primer for abrasive cloth, cloth-based treatment for abrasive cloth or filter paper impregnation.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011587398.5A CN112661978A (en) | 2020-12-29 | 2020-12-29 | Emulsifiable low-aldehyde environment-friendly water-based phenolic resin and preparation method and application thereof |
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| CN202011587398.5A CN112661978A (en) | 2020-12-29 | 2020-12-29 | Emulsifiable low-aldehyde environment-friendly water-based phenolic resin and preparation method and application thereof |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3956204A (en) * | 1975-03-10 | 1976-05-11 | Monsanto Company | Antipunking phenolic resin binder systems for mineral fiber thermal insulation |
| US5371140A (en) * | 1992-11-25 | 1994-12-06 | Georgia-Pacific Resins, Inc. | Emulsifiable phenolic resole resin |
| US5708121A (en) * | 1995-02-22 | 1998-01-13 | Georgia-Pacific Resins, Inc. | Storage stable melamine-modified phenolic resole resins using an alkaline condensation and polyhydroxyl compound stabilization |
| WO1999060042A1 (en) * | 1998-05-18 | 1999-11-25 | Rockwool International A/S | Stabilized aqueous phenolic binder for mineral wool and production of mineral wool products |
| US20020188030A1 (en) * | 2001-06-08 | 2002-12-12 | Peter Ziegler | Externally emulsified aqueous resole dispersions |
| CN104005261A (en) * | 2014-05-12 | 2014-08-27 | 华东理工大学 | Modified waterborne phenolic resin for automobile engine oil filter paper and preparation method thereof |
| CN110004760A (en) * | 2019-02-13 | 2019-07-12 | 浙江杭摩合成材料股份有限公司 | The production technology of compound emulsifying agent, phenolic resin aqueous emulsion and paper friction material |
-
2020
- 2020-12-29 CN CN202011587398.5A patent/CN112661978A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3956204A (en) * | 1975-03-10 | 1976-05-11 | Monsanto Company | Antipunking phenolic resin binder systems for mineral fiber thermal insulation |
| US5371140A (en) * | 1992-11-25 | 1994-12-06 | Georgia-Pacific Resins, Inc. | Emulsifiable phenolic resole resin |
| US5708121A (en) * | 1995-02-22 | 1998-01-13 | Georgia-Pacific Resins, Inc. | Storage stable melamine-modified phenolic resole resins using an alkaline condensation and polyhydroxyl compound stabilization |
| WO1999060042A1 (en) * | 1998-05-18 | 1999-11-25 | Rockwool International A/S | Stabilized aqueous phenolic binder for mineral wool and production of mineral wool products |
| US20020188030A1 (en) * | 2001-06-08 | 2002-12-12 | Peter Ziegler | Externally emulsified aqueous resole dispersions |
| CN104005261A (en) * | 2014-05-12 | 2014-08-27 | 华东理工大学 | Modified waterborne phenolic resin for automobile engine oil filter paper and preparation method thereof |
| CN110004760A (en) * | 2019-02-13 | 2019-07-12 | 浙江杭摩合成材料股份有限公司 | The production technology of compound emulsifying agent, phenolic resin aqueous emulsion and paper friction material |
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