CN1557851A - Shell-core polymer containing phenolic resin and use thereof - Google Patents
Shell-core polymer containing phenolic resin and use thereof Download PDFInfo
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- CN1557851A CN1557851A CNA2004100159974A CN200410015997A CN1557851A CN 1557851 A CN1557851 A CN 1557851A CN A2004100159974 A CNA2004100159974 A CN A2004100159974A CN 200410015997 A CN200410015997 A CN 200410015997A CN 1557851 A CN1557851 A CN 1557851A
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Abstract
The phenolic resin containing core-shell polymer may be used in resin grinding wheel, braking friction sheet, molded phenolic plastic and fiber reinforced phenolic resin composite material. The present invention provides the preparation process of molded plastic with the resin. Especially, the molded plastic includes phenolic resin with core-shell polymer, linear phenolic resin, hexamethine tetramine, lower molecular weight polyolefin, cure promoter, stuffing, and short cut fiber or mixed organic-inorganic fiber. The method of the present invention is economic, simple and suitable for industrial production.
Description
Technical field
The present invention relates to a kind of resol preparation method.More particularly relate to contain the resol preparation method and the application of nuclear-shell polymeric.
Background technology
Resol have unique heat-resisting, difficult combustion and lowly be fuming, premium properties such as electric insulation, mechanical property height and dimensional stability are good, has significant ratio of performance to price advantage, therefore, make it to be widely used in fields such as machinery, electronics, communications and transportation, building materials, national defence, as tackiness agent, friction element, industry and decorative laminate, moulding compound and fibre reinforced composites.
Although resol has excellent properties such as unique thermotolerance, flame retardancy, electric insulating quality, mechanical property height and dimensional stability be good,, cause its shock-resistance and snappiness relatively poor because of himself inherent structural performance and cured article cross-linking density height.Therefore, improve the fragility of resol, improving its shock-resistance and snappiness is the target that present most of resol manufacturing and application department are pursued.The toughness that improves resol mainly contains following several approach: plasticizing substance outside (1) adds in resol, as natural rubber, paracril, styrene-butadiene rubber(SBR) and thermoplastic resin etc.; (2) add the intrinsic toughening material in resol, as the phenolic hydroxyl group etherificate, at the long methene chain of the internuclear introducing of phenol and other flexible groups etc., though these methods have improved toughness, thermotolerance has descended.Simultaneously because preparation technology's complicacy has improved the industrial production cost.Add wood powder, or other enhancement component are also undesirable with the effect of the mouldable heat-reactive phenolic resin composition of the flexible that is improved, and are difficult to satisfy the requirement of electrical apparatus industry to the impact resistance index of alkyd resin moulding material.Therefore, the toughening modifying problem of resol is a focus of current resol development and application always.
Utilize in tung oil, the oleum lini equimolecular the two keys of abundant common Yoke, import phenol earlier, carry out the Diels-Alder addition reaction, carry out condensation reaction with formaldehyde again and can prepare and have certain flexible resol.The patent of utilizing this principle to prepare modified phenolic resins mainly contains, Hitachi changes into the (JP60-22850A of industrial, JP61-21122A) method of tung oil modified phenolic resin was once disclosed, Wang Li units of Beijing Normal University etc. are at Chinese patent CN88101351,91103376, tung oil is disclosed in 97112373, eleostearic acid, the method of maleimide-tung oil modified phenolic resin, vow that wild text etc. is at Chinese patent CN93117228,95109859, disclose in 97109279 with the method for plant oil modified phenol-formaldehyde resin as tackiness agent prepared layer pressboard, Lie group is at Chinese patent CN91107262, disclose the method for preparing the friction brake sheet with tung oil modified phenolic resin in 91108338, the above-mentioned method of obtaining the snappiness phenol resin composition has been represented thermotolerance, flame resistivity and chemical proofing, a kind of compromise between the reduction of dimensional stability and toughness improve.
Yin Jinghua etc. are at Chinese patent CN92104924, paracril is disclosed in 87101016, the polyvinyl acetal modified phenolic resins prepares the method for friction brake sheet as tackiness agent, G.S. the Metcalfe discloses nitrile rubber modified phenolic resin and has prepared the method for rocket engine shell with ablative thermal barrier in Chinese patent CN010815434, clear and the triumphant grace of J.F. of Cheng Zehong is at Chinese patent CN01802336, the polysiloxane-modified phenolic resin-made that discloses alkoxyl group or silanol-functional in 96194806 has been got everything ready and has been improved shock-resistance and thermotolerance phenol resin composition, above method complicated process of preparation, the production cost height.Be not suitable for preparing phenolaldehyde moulding compound.
Time is prolonged pardon to wait and is disclosed butadiene-styrene latex modified phenol-formaldehyde resin prepare the method for friction brake sheet as tackiness agent in Chinese patent CN86104223, and this method is simple for process, and the wear resisting property and the toughness of gained friction brake sheet all improve.Viacent R.Landi discloses paracril can improve phenolaldehyde moulding compound significantly under the effect of sulphur high temperature resistant aging resistance in United States Patent (USP) 4725650.Aforesaid method be difficult for to realize that in resol manufacturer this is because the divinylic monomer boiling point is low, and the butyronitrile latex polymerization needs to depress at low temperature or band to be carried out, and has increased facility investment.
Summary of the invention
The purpose of this invention is to provide a kind of resol that contains nuclear-shell polymeric, and use it and made a kind of alkyd resin moulding material that contains nuclear-shell polymeric.
Technical scheme is as follows:
A kind of resol that contains nuclear-shell polymeric, its raw material and content following (weight part):
Ionized water 120
Sodium lauryl sulphate 1.0
Lauryl mercaptan 0.3
Potassium Persulphate 0.1
Vinylstyrene 0.8
Acrylate 39.2
Vinyl cyanide 57.0
Vinylformic acid 2.0
Hydroxyl acrylic ethyl ester 1.0
Phenol 1
Formaldehyde 1.8～2.5
Catalyzer 0.008
Deionized water, sodium lauryl sulphate, lauryl mercaptan, Potassium Persulphate, Vinylstyrene and acrylate are mixed according to the above ratio, add reactor, warming while stirring is to 70-75 ℃; When monomer conversion reaches 95%, after the temporary transient cooling; Add vinyl cyanide, vinylformic acid, hydroxy acrylate according to the above ratio and be warming up to 70-75 ℃, continue reaction to monomeric transformation efficiency and reach 95%, cooling finishes reaction; Phenol, formaldehyde, catalyzer are added reactor according to the above ratio, stir and be warmed up to 80-100 ℃, reacted 4-5 hour, vacuum hydro-extraction promptly obtains a kind of resol that contains nuclear-shell polymeric;
Wherein: described catalyzer is hydrochloric acid, oxalic acid and zinc acetate compound system.
The particle diameter of the above-mentioned resol that contains nuclear-shell polymeric is between 100～850nm.
A kind of alkyd resin moulding material that contains nuclear-shell polymeric, its raw material and content (weight part) are as follows:
The resol 50.0 that contains nuclear-shell polymeric
Lacquer resins 50.0
Hexamethylenetetramine 5.0
Molecular weight is a 500-1500 polyolefine 2.0
Calcium hydroxide 1.0
Lime carbonate 25.0
Glass fibre 25.0
With above-mentioned raw materials, according to the above ratio, usefulness is rolled machine, the twin screw kneader makes the alkyd resin moulding material that contains nuclear-shell polymeric.
Described linear phenolic resin is that softening temperature is between 85-95 ℃ by the resol of hydrochloric acid catalysis preparation.
The present invention has following advantage: preparation process is simple, help reducing the industrial production cost, be convenient to realize industrialization, gained resol is of many uses, be particularly useful for making phenolaldehyde moulding compound and phenolic aldehyde pultrusion product, have excellent mouldability and rapidly-curable.Make goods toughness by it and improve, the high temperature ageing-resistant performance is improved.
Specific implementation method
The present invention is by following examples, but the cited case does not limit content of the present invention.
Embodiment 1:
At first 120g deionized water, 1.0g sodium lauryl sulphate, 0.3g lauryl mercaptan, 0.1g Potassium Persulphate and 39.2g butyl acrylate, 0.8g Vinylstyrene are added reactor, after stirring, warming while stirring to 70 ℃; When monomeric transformation efficiency reaches 95%, after the temporary transient cooling, once add 57.0g vinyl cyanide, 2.0g vinylformic acid, 1.0g hydroxy acrylate, continue reaction to monomeric transformation efficiency down at 70 ℃ and reach 95%, cooling finishes reaction.Second step added reactor with phenol, formaldehyde, catalyzer, stirred and be warmed up to 80 ℃, reacted 4 hours, and vacuum hydro-extraction promptly obtains containing the resol of nuclear-shell polymeric.
Embodiment 2
At first 120g deionized water, 1.0g sodium lauryl sulphate, 0.3g lauryl mercaptan, 0.1g Potassium Persulphate and 39.2g butyl acrylate, 0.8g Vinylstyrene are added reactor, after stirring, warming while stirring to 75 ℃; When monomeric transformation efficiency reached 95%, after the temporary transient cooling, adding 57.0g vinyl cyanide, 2.0g vinylformic acid, 1.0g hydroxy acrylate were warming up to 75 ℃, continued reaction to monomeric transformation efficiency and reached 95%, cooling, end reaction.Second step added reactor with phenol, formaldehyde, catalyzer, stirred and be warmed up to 100 ℃, reacted 5 hours, and vacuum hydro-extraction promptly obtains containing the resol of nuclear-shell polymeric.
Embodiment 3
At first 120g deionized water, 1.0g sodium lauryl sulphate, 0.3g lauryl mercaptan, 0.1g Potassium Persulphate and 39.2g butyl acrylate, 0.8g Vinylstyrene are added reactor, after stirring, warming while stirring to 75 ℃; When monomeric transformation efficiency reaches 95%, after the temporary transient cooling, add the 57.0g vinyl cyanide, be warming up to 75 ℃, continue reaction to monomeric transformation efficiency and reach 95%, cooling finishes reaction.Second step added reactor with phenol, formaldehyde, catalyzer, stirred and be warmed up to 100 ℃, reacted 5 hours, and vacuum hydro-extraction promptly obtains containing the resol of nuclear-shell polymeric.
Embodiment 4
At first 120g deionized water, 1.0g sodium lauryl sulphate, 0.3g lauryl mercaptan, 0.1g Potassium Persulphate and 39.2g butyl acrylate, 0.8g Vinylstyrene are added reactor, after stirring, warming while stirring to 70 ℃; When monomeric transformation efficiency reaches 95%, after the temporary transient cooling, add 57.0g vinyl cyanide, 2.0g vinylformic acid, 1.0g hydroxy acrylate continuously, continue reaction to monomeric transformation efficiency down at 70-75 ℃ and reach 95%, cooling finishes reaction.Cooling finishes reaction.Second step added another reactor with phenol, formaldehyde, catalyzer, stirred and be warmed up to 90 ℃, reacted 4 hours, the resol that the nuclear-shell polymeric latex that the first step is obtained and second step obtain is put into same reactor, and vacuum hydro-extraction promptly obtains containing the resol of nuclear-shell polymeric.
Embodiment 5
A kind of composition that contains the alkyd resin moulding material of nuclear-shell polymeric: contain resol, lacquer resins, hexamethylenetetramine, low-molecular-weight polyolefin, curing catalyst, short glass fiber or the organic-inorganic assorted fibre of nuclear-shell polymeric, preparation process forms for mediating with the methods such as machine, twin screw kneader of rolling.
Table 1
Embodiment 1 embodiment 2 embodiment 3 embodiment 4
The particle diameter 180nm 240nm 265nm 385nm of nuclear-shell polymeric
The gelation time of resin
(sec/165℃) 65 72 95 85
Claims (4)
1, a kind of resol that contains nuclear-shell polymeric is characterized in that, described raw material and the content following (weight part) that contains the resol of nuclear-shell polymeric:
Ionized water 120
Sodium lauryl sulphate 1.0
Lauryl mercaptan 0.3
Potassium Persulphate 0.1
Vinylstyrene 0.8
Acrylate 39.2
Vinyl cyanide 57.0
Vinylformic acid 2.0
Hydroxyl acrylic ethyl ester 1.0
Phenol 1
Formaldehyde or Paraformaldehyde 96 1.8～2.5
Catalyzer 0.008
Deionized water, sodium lauryl sulphate, lauryl mercaptan, Potassium Persulphate, Vinylstyrene and acrylate are mixed according to the above ratio, add reactor, warming while stirring is to 70-75 ℃; When monomer conversion reaches 95%, after the temporary transient cooling; Add vinyl cyanide, vinylformic acid, hydroxy acrylate according to the above ratio and be warming up to 70-75 ℃, continue reaction to monomeric transformation efficiency and reach 95%, cooling finishes reaction; Phenol, formaldehyde, catalyzer are added reactor according to the above ratio, stir and be warmed up to 80-100 ℃, reacted 4-5 hour, vacuum hydro-extraction promptly obtains a kind of resol that contains nuclear-shell polymeric;
Wherein: described catalyzer is hydrochloric acid, oxalic acid and zinc acetate compound system.
2, the nuclear-shell polymeric that contains as claimed in claim 1 is characterized in that, the particle diameter of resol that contains nuclear-shell polymeric is between 100～850nm.
3, a kind of alkyd resin moulding material that contains nuclear-shell polymeric is characterized in that, the raw material of described phenolic plastics and content (weight part) are as follows:
The resol 50.0 that contains nuclear-shell polymeric
Lacquer resins 50.0
Hexamethylenetetramine 5.0
Molecular weight is a 500-1500 polyolefine 2.0
Calcium hydroxide 1.0
Lime carbonate 25.0
Glass fibre 25.0
With above-mentioned raw materials, according to the above ratio, usefulness is rolled machine, the twin screw kneader makes the alkyd resin moulding material that contains nuclear-shell polymeric.
4, a kind of alkyd resin moulding material that contains nuclear-shell polymeric as claimed in claim 3 is characterized in that, described linear phenolic resin is that softening temperature is between 85-95 ℃ by the resol of hydrochloric acid catalysis preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410015997 CN1259355C (en) | 2004-01-19 | 2004-01-19 | Shell-core polymer containing phenolic resin and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410015997 CN1259355C (en) | 2004-01-19 | 2004-01-19 | Shell-core polymer containing phenolic resin and use thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1557851A true CN1557851A (en) | 2004-12-29 |
| CN1259355C CN1259355C (en) | 2006-06-14 |
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| CN 200410015997 Expired - Fee Related CN1259355C (en) | 2004-01-19 | 2004-01-19 | Shell-core polymer containing phenolic resin and use thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045968A (en) * | 2014-06-19 | 2014-09-17 | 同济大学 | Flexible kernel hard shell polymer kernel-inorganic shell nanocomposite particle material toughened phenolic foam |
| CN104169362A (en) * | 2012-03-29 | 2014-11-26 | 三井化学株式会社 | Phenolic resin molding material, friction material, and phenolic resin molded article |
| CN114015195A (en) * | 2021-11-22 | 2022-02-08 | 山东北方现代化学工业有限公司 | Nano calcium carbonate modified thermosetting phenolic resin reinforced composite material for die pressing and preparation method thereof |
-
2004
- 2004-01-19 CN CN 200410015997 patent/CN1259355C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104169362A (en) * | 2012-03-29 | 2014-11-26 | 三井化学株式会社 | Phenolic resin molding material, friction material, and phenolic resin molded article |
| CN104169362B (en) * | 2012-03-29 | 2016-03-16 | 三井化学株式会社 | Phenol resin molding material, friction material and phenol resins products formed |
| US9505925B2 (en) | 2012-03-29 | 2016-11-29 | Mitsui Chemicals, Inc. | Phenol resin molding material, friction material, and phenol resin molded product |
| CN104045968A (en) * | 2014-06-19 | 2014-09-17 | 同济大学 | Flexible kernel hard shell polymer kernel-inorganic shell nanocomposite particle material toughened phenolic foam |
| CN104045968B (en) * | 2014-06-19 | 2015-11-25 | 同济大学 | A kind of soft core crust polymer core-inorganic shell nano-complex particle material toughening metlbond foam |
| CN114015195A (en) * | 2021-11-22 | 2022-02-08 | 山东北方现代化学工业有限公司 | Nano calcium carbonate modified thermosetting phenolic resin reinforced composite material for die pressing and preparation method thereof |
| CN114015195B (en) * | 2021-11-22 | 2023-06-30 | 山东北方现代化学工业有限公司 | Nano calcium carbonate modified thermosetting phenolic resin reinforced composite material for mould pressing and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1259355C (en) | 2006-06-14 |
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