CN103724935B - A kind of method of urea-formaldehyde resin toughening modifying - Google Patents
A kind of method of urea-formaldehyde resin toughening modifying Download PDFInfo
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Abstract
A kind of method of urea-formaldehyde resin toughening modifying, comprise the following steps: toughner acrylic polymer, vinylic polymers or acetals polymkeric substance and urea-formaldehyde resin mixed by dispersing apparatus and obtain urea-formaldehyde resin Moulding powder, the ratio that wherein toughner acrylic polymer, vinylic polymers or acetals polymkeric substance account for mixture quality is no more than 80%; With vulcanizing press by 60 ~ 200 order urea-formaldehyde resin Moulding powder at 80 ~ 200 DEG C, suppress 2 ~ 20min under 5 ~ 60MPa condition, obtained impact batten or bending batten.The present invention homemade toughner acrylic polymer or commercially available acetals polymkeric substance or vinylic polymers carry out toughening modifying to urea-formaldehyde resin, and wherein, best with homemade acrylic polymer toughening effect, shock strength is 2.50kJ/m
2, flexural strength is 85MPa.
Description
Technical field
The present invention relates to the method for toughening of aminoresin Moulding powder, the method for the acrylic polymer specifically prepared with oneself or vinylic polymers or acetals polymer toughening urea-formaldehyde resin.
Background technology
Urea-formaldehyde resin moulding material is the insoluble not molten thermosetting material be made up through operations such as plasticizing processing and compression moldings of a series of auxiliary agent such as urea-formaldehyde resin, weighting agent and solidifying agent, expanding material, lubricant, staining agent.The product color of this material produce is bright-coloured, smooth in appearance, gathers around and have great advantage in alternative common plastics, domestic ceramics, timber and metallic substance etc.CN101113230A provides a kind of method that unsaturated polyester cross-linking waste prepares moulding compound: by glass reinforced plastic, the unsaturated polyester wastes such as button waste material after crushed, with thermosetting resin as epoxy resin, aminoresin etc. press certain mass than mixing, wherein unsaturated polyester waste powder accounts for 60 ~ 95% quality, then with polymer in-mold press forming devices such as vulcanizing presses, compression molding is carried out to mixed powder, obtain the moulding compound of high unsaturated polyester waste content, the material mechanical performance of preparation is improved, but the method shortcoming is that unsaturated polyester is without surface treatment, obtained moulding compound can only be used for producing low-end product.Han Chunguo etc. add 1.0 ~ 3.0%(massfraction) polyethylene glycol 6000 time, the urea-formaldehyde resin shock strength of preparation is 1.63 ~ 1.75kJ/m
2, it is not clearly (Han Chunguo, Li Shouhai, Wang Chunpeng, etc., softening agent on the impact of urea-formaldehyde resin moulding compound performance, modern chemical industry, 2011,31(2) that shock strength improves: 61-65).The object of the invention is, while raising aminoresin toughness, to promote the Application Areas of aminoresin.
Summary of the invention
the technical problem solved:low in order to solve the urea-formaldehyde resin moulding compound intensity existed in prior art, the shortcomings such as poor toughness, the invention provides a kind of method of urea-formaldehyde resin toughening modifying, obtained molded test has the advantage such as high strength, high tenacity.
technical scheme:a kind of method of urea-formaldehyde resin toughening modifying, comprise the following steps: toughner acrylic polymer, vinylic polymers or acetals polymkeric substance and urea-formaldehyde resin mixed by dispersing apparatus and obtain urea-formaldehyde resin Moulding powder, the ratio that wherein toughner acrylic polymer, vinylic polymers or acetals polymkeric substance account for mixture quality is no more than 80%; With vulcanizing press by 60 ~ 200 order urea-formaldehyde resin Moulding powder at 80 ~ 200 DEG C, suppress 2 ~ 20min under 5 ~ 60MPa condition, obtained impact batten or bending batten; The preparation method of described toughner acrylic polymer is: emulsifying agent and water are added in pre-emulsification still, wherein in pre-emulsification still, the add-on of water is prepare acrylic polymer water total mass 20% ~ 40%, again by soft, hard monomer in mass ratio (1 ~ 12): (20 ~ 6) are added drop-wise in pre-emulsification still when stirring, stirred at ambient temperature 0.5 ~ 5h makes pre-emulsion, and wherein soft or hard monomer total mass used is 3/7 ~ 7/3 with the ratio preparing acrylic polymer water total mass; Get emulsifying agent again and water is added in reactor, in reactor, the consumption of water is prepare acrylic polymer water total mass 60% ~ 80%, then getting 1/20 ~ 1/10 of pre-emulsion total mass is added in the aqueous phase of this reactor, and initiator is added in remaining pre-emulsion, initiator amount is 0.1% ~ 5% of added monomer total mass; The total consumption of emulsifying agent is 0.1% ~ 6% of monomer total mass, and wherein primary emulsifying agent consumption is 1 ~ 20:1 with the mass ratio of second time consumption; The pre-emulsion adding initiator is added drop-wise in reactor when being warming up to 50 DEG C ~ 100 DEG C by reactor, drips off at 2 ~ 6h, and after insulation 0.5 ~ 4h, cooling is filtered and obtains emulsion; The emulsion of preparation is dry at 30 ~ 80 DEG C, be crushed to 60 ~ 200 orders with pulverizer, obtain acrylic polymer toughner.
Described vinylic polymers is at least one in polystyrene, polyvinyl alcohol, ethylene-vinyl acetate multipolymer, polyvinyl acetate copolymer, ethene-vinyl acetate-vinyl versatate copolymer.
Described acetals polymkeric substance be polyvinyl formal, polyvinylacetal, polyvinyl formal acetal, polyvinyl butyral acetal, vinyl acetal base polymer, contracting oxalic dialdehyde, cardanol aminal, acetal urushiol amine, at least one in aromatic diacid ester acetal polymer.
Described emulsifying agent is at least one in polyoxyethylene nonylphenol ether (OP), polyvinyl alcohol-200, polyoxyethylene octylphenol ether maleic acid ester sodium (OS), sodium stearate, sodium lauryl sulphate (SDS), dehydrogenation potassium rosinate, sodium dibutyl naphthalene sulfonate.
Described initiator is ammonium persulphate, Diisopropyl azodicarboxylate, different phenylpropyl alcohol hydrogen peroxide, peroxidized t-butyl perbenzoate, dibenzoyl peroxide, cyclohexanone peroxide, naphthoic acid are cuprous, triethyl aluminum, DMA, S-WAT, oxalic acid, the polymerization degree are at least one in the polyoxyethylene phenolic ether in the ninth of the ten Heavenly Stems of 16.
Described soft monomer is at least one in n-butyl acrylate, amyl acrylate, glycidyl methacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, isobutyl acrylate, tert-butyl acrylate; Hard monomer is at least one in vinylformic acid, vinyl cyanide, methyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, N methacrylamide, ethyl propenoate.
Described dispersing apparatus is at least one in pulverizer, mill, Banbury mixer, kneader.
beneficial effect:
1. acrylic polymer preparation method simple possible in the present invention;
2. the present invention adopts the method toughening modifying urea-formaldehyde resin of physical blending, and operating process Simple And Practical, is easy to industrialization;
3. the present invention's homemade toughner acrylic polymer or commercially available acetals polymkeric substance or vinylic polymers carries out toughening modifying to urea-formaldehyde resin, and wherein, best with homemade acrylic polymer toughening effect, shock strength is 2.50kJ/m
2, flexural strength is 85MPa.
Embodiment
Below in conjunction with concrete example, illustrate the solution of the present invention and effect further.
embodiment 1:
(1) pre-emulsification: in pre-emulsification still, the emulsifier mixture of 1.35gOP, 0.90g sodium stearate and 0.25gSDS is added in 250g deionized water, again 180g soft monomer n-butyl acrylate, 20g Hydroxyethyl acrylate and 282g methyl methacrylate, 18g methacrylic acid hard monomer are added drop-wise in aqueous phase under agitation, churning time is 4h, makes pre-emulsion.
(2) seeded emulsion polymerization: in reactor, get 0.35g polyoxyethylene nonylphenol ether and 0.15g sodium dibutyl naphthalene sulfonate to be added in 480g water and to form aqueous phase, getting 75g pre-emulsion is added in aqueous phase, when being warming up to 85 DEG C, the residue pre-emulsion 3h adding 2.50g initiator ammonium persulfate is added drop-wise to polyreaction in reactor, filters after being down to room temperature after insulation 1h and obtain emulsion.
(3) toughness reinforcing urea-formaldehyde resin: the emulsion of above-mentioned preparation is dry at 40 DEG C, be crushed to 140 orders with pulverizer and obtain acrylic ester polymer, this polymkeric substance of 20g is mixed obtained modification Moulding powder with 80g urea-formaldehyde resin kneader, get 60g modification Moulding powder at 165 DEG C, shaping with vulcanizing press mold pressing 10min under 30MPa condition, the urea-formaldehyde resin of obtained certain size impacts batten (band breach); Get 20g modification Moulding powder at 160 DEG C, under 25MPa, mold pressing 6min is shaping, and the modified urea-formaldehyde resin of obtained certain size bends batten.
The impact that the present embodiment prepares and crooked test batten fundamental property the results are shown in subordinate list 1, and subordinate list 1 is the fundamental performance parameter of each toughner toughening modifying urea-formaldehyde resin moulding compound in various embodiments of the present invention.
embodiment 2:
(1) emulsion preparation: in pre-emulsification, emulsifying agent used is 5.50g polyvinyl alcohol-200 and 7.50gOS emulsifier mixture.75g soft monomer amyl acrylate and 20g vinyl cyanide, 375g β-dimethyl-aminoethylmethacrylate, 30gN-methyl acrylamide monomer are added drop-wise in pre-emulsification still after mixing, get in the aqueous phase that 75g pre-emulsion is added to containing 1.00g polyoxyethylene nonylphenol ether and 1.20gSDS, when being warming up to 95 DEG C, the residue pre-emulsion 5h adding 3.50g initiator peroxidized t-butyl perbenzoate and 6.50g dibenzoyl peroxide is added drop-wise to polyreaction in reactor, filters after being down to room temperature after insulation 0.5h and obtain emulsion.Other recipe optimization are identical with embodiment 1.
(2) toughness reinforcing urea-formaldehyde resin: the emulsion of above-mentioned preparation is dry at 50 DEG C, be crushed to 100 orders with pulverizer and obtain acrylic ester polymer, this polymkeric substance of 35g is mixed obtained modification Moulding powder with 65g urea-formaldehyde resin kneader, get 60g modification Moulding powder at 120 DEG C, shaping with vulcanizing press mold pressing 16min under 40MPa condition, the urea-formaldehyde resin of obtained certain size impacts batten (band breach); Get 20g modification Moulding powder at 115 DEG C, under 45MPa, mold pressing 7min is shaping, and the modified urea-formaldehyde resin of obtained certain size bends batten.
The impact that the present embodiment prepares and crooked test batten fundamental property the results are shown in subordinate list 1.
embodiment 3:
(1) emulsion preparation: in pre-emulsification, emulsifying agent used is 0.40gSDS, 0.20g dehydrogenation potassium rosinate and 0.15g sodium dibutyl naphthalene sulfonate mixture.Be added drop-wise in pre-emulsification still after 250g soft monomer amyl acrylate, 30g glycidyl methacrylate and 170g methyl acrylate, the mixing of 50gN-Methacrylamide hard monomer, get in the aqueous phase that 75g pre-emulsion is added to containing emulsifying agent 0.10gOP and 0.15g sodium dibutyl naphthalene sulfonate, when being warming up to 55 DEG C by adding initiator 0.33g cyclohexanone peroxide, 0.28g naphthoic acid residue pre-emulsion 2h that is cuprous and 0.39g triethyl aluminum is added drop-wise to polyreaction in reactor, filter after being down to room temperature after insulation 3.5h and obtain emulsion.Other recipe optimization are identical with embodiment 1.
(2) toughness reinforcing urea-formaldehyde resin: the emulsion of above-mentioned preparation is dry at 50 DEG C, be crushed to 150 orders with pulverizer and obtain acrylic ester polymer, this polymkeric substance of 55g is mixed obtained modification Moulding powder with the mill of 45g urea-formaldehyde resin, get 60g modification Moulding powder at 180 DEG C, shaping with vulcanizing press mold pressing 8min under 20MPa condition, the urea-formaldehyde resin of obtained certain size impacts batten (band breach); Get 20g modification Moulding powder at 175 DEG C, under 20MPa, mold pressing 7min is shaping, and the modified urea-formaldehyde resin of obtained certain size bends batten.
The impact that the present embodiment prepares and crooked test batten fundamental property the results are shown in subordinate list 1.
embodiment 4:
10g polystyrene and the blended evenly obtained Moulding powder of 90g120 object urea-formaldehyde resin kneader.Get 60g modification Moulding powder at 175 DEG C, shaping with vulcanizing press mold pressing 11min under 30MPa condition, the urea-formaldehyde resin of obtained certain size impacts batten (band breach); Get 20g modification Moulding powder at 170 DEG C, under 35MPa, mold pressing 4min is shaping, and the modified urea-formaldehyde resin of obtained certain size bends batten.
The impact that the present embodiment prepares and crooked test batten fundamental property the results are shown in subordinate list 1.
embodiment 5:
40g ethylene-vinyl acetate multipolymer and the blended evenly obtained Moulding powder of 60g180 object urea-formaldehyde resin Banbury mixer.Get 60g modification Moulding powder at 90 DEG C, shaping with vulcanizing press mold pressing 18min under 60MPa condition, the urea-formaldehyde resin of obtained certain size impacts batten (band breach); Get 20g modification Moulding powder at 85 DEG C, under 55MPa, mold pressing 10min is shaping, and the modified urea-formaldehyde resin of obtained certain size bends batten.
The impact that the present embodiment prepares and crooked test batten fundamental property the results are shown in subordinate list 1.
embodiment 6:
70g polyvinyl formal acetal and the blended evenly obtained Moulding powder of 30g80 object urea-formaldehyde resin kneader.Get the Moulding powder that 60g mixes, get 60g modification Moulding powder at 140 DEG C, shaping with vulcanizing press mold pressing 14min under 55MPa condition, the urea-formaldehyde resin of obtained certain size impacts batten (band breach); Get 20g modification Moulding powder at 135 DEG C, under 45MPa, mold pressing 5min is shaping, and the modified urea-formaldehyde resin of obtained certain size bends batten.
The impact that the present embodiment prepares and crooked test batten fundamental property the results are shown in subordinate list 1.
embodiment 7;
50g aromatic diacid ester acetal polymer mixes obtained Moulding powder with 50g120 object urea-formaldehyde resin pulverizer.Get the Moulding powder that 60g mixes, get 60g modification Moulding powder at 195 DEG C, shaping with vulcanizing press mold pressing 8min under 20MPa condition, the urea-formaldehyde resin of obtained certain size impacts batten (band breach); Get 20g modification Moulding powder at 190 DEG C, under 15MPa condition, mold pressing 3min is shaping, and the modified urea-formaldehyde resin of obtained certain size bends batten.
The impact that the present embodiment prepares and crooked test batten fundamental property the results are shown in subordinate list 1.
Subordinate list 1: the fundamental performance parameter of the toughness reinforcing urea-formaldehyde resin Moulding powder of each toughner
Note: according to GB13454-92, urea-formaldehyde resin shock strength>=2.0kJ/m
2, flexural strength>=80MPa can reach premium grads; Urea-formaldehyde resin shock strength>=1.70kJ/m
2, flexural strength>=70MPa can reach Eligibility requirements; "-" represents mold pressing batten can not be shaping, cannot detect.
Subordinate list 1 result shows, the esters of acrylic acid toughner toughness reinforcing urea-formaldehyde resin effect of embodiment 1 of the present invention is more excellent.
Above-mentioned flexural strength test uses SANSCMT Series Microcomputer to control electronic universal tester (Shenzhen Sans Material Detection Co., Ltd); Test shock strength uses XJJY-5 liquid-crystal display impact tester for simple supported beam (Chengde Xin Guo test set company limited).
Claims (5)
1. a method for urea-formaldehyde resin toughening modifying, is characterized in that, comprises the following steps:
Toughner acrylic polymer, vinylic polymers or acetals polymkeric substance and urea-formaldehyde resin mixed by dispersing apparatus and obtain urea-formaldehyde resin Moulding powder, the ratio that wherein toughner acrylic polymer, vinylic polymers or acetals polymkeric substance account for mixture quality is no more than 80%; With vulcanizing press by 60 ~ 200 order urea-formaldehyde resin Moulding powder at 80 ~ 200 DEG C, suppress 2 ~ 20min under 5 ~ 60MPa condition, obtained impact batten or bending batten; Described vinylic polymers is at least one in polystyrene, polyvinyl alcohol, ethylene-vinyl acetate multipolymer, polyvinyl acetate copolymer, ethene-vinyl acetate-vinyl versatate copolymer;
The preparation method of described toughner acrylic polymer is: emulsifying agent and water are added in pre-emulsification still, wherein in pre-emulsification still, the add-on of water is prepare acrylic polymer water total mass 20% ~ 40%, again by soft monomer, hard monomer in mass ratio (1 ~ 12): (20 ~ 6) are added drop-wise in pre-emulsification still when stirring, stirred at ambient temperature 0.5 ~ 5h makes pre-emulsion, and wherein soft monomer used and hard monomer total mass are 3/7 ~ 7/3 with the ratio preparing acrylic polymer water total mass; Get emulsifying agent again and water is added in reactor, in reactor, the consumption of water is prepare acrylic polymer water total mass 60% ~ 80%, then getting 1/20 ~ 1/10 of pre-emulsion total mass is added in the aqueous phase of this reactor, and initiator is added in remaining pre-emulsion, initiator amount is 0.1% ~ 5% of added monomer total mass; The total consumption of emulsifying agent is 0.1% ~ 6% of monomer total mass, and wherein primary emulsifying agent consumption is 1 ~ 20:1 with the mass ratio of second time consumption; The pre-emulsion adding initiator is added drop-wise in reactor when being warming up to 50 DEG C ~ 100 DEG C by reactor, drips off at 2 ~ 6h, and after insulation 0.5 ~ 4h, cooling is filtered and obtains emulsion; The emulsion of preparation is dry at 30 ~ 80 DEG C, be crushed to 60 ~ 200 orders with pulverizer, obtain acrylic polymer toughner; Described soft monomer is at least one in n-butyl acrylate, amyl acrylate, glycidyl methacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, isobutyl acrylate, tert-butyl acrylate; Hard monomer is at least one in vinylformic acid, vinyl cyanide, methyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, N methacrylamide, ethyl propenoate.
2. the method for urea-formaldehyde resin toughening modifying according to claim 1, it is characterized in that described acetals polymkeric substance be polyvinyl formal, polyvinylacetal, polyvinyl formal acetal, polyvinyl butyral acetal, vinyl acetal base polymer, contracting oxalic dialdehyde, cardanol aminal, acetal urushiol amine, at least one in aromatic diacid ester acetal polymer.
3. the method for urea-formaldehyde resin toughening modifying according to claim 1, is characterized in that described emulsifying agent is at least one in polyoxyethylene nonylphenol ether, polyvinyl alcohol-200, polyoxyethylene octylphenol ether maleic acid ester sodium, sodium stearate, sodium lauryl sulphate, dehydrogenation potassium rosinate, sodium dibutyl naphthalene sulfonate.
4. the method for urea-formaldehyde resin toughening modifying according to claim 1, it is characterized in that described initiator is ammonium persulphate, Diisopropyl azodicarboxylate, different phenylpropyl alcohol hydrogen peroxide, peroxidized t-butyl perbenzoate, dibenzoyl peroxide, cyclohexanone peroxide, naphthoic acid are cuprous, triethyl aluminum, DMA, S-WAT, oxalic acid, the polymerization degree are at least one in the polyoxyethylene phenolic ether in the ninth of the ten Heavenly Stems of 16.
5. the method for urea-formaldehyde resin toughening modifying according to claim 1, is characterized in that described dispersing apparatus is at least one in pulverizer, mill, Banbury mixer, kneader.
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| CN105885320B (en) * | 2016-06-13 | 2018-02-06 | 上海金山锦湖日丽塑料有限公司 | A kind of PMMA resins with superhigh tenacity |
| CN108456404A (en) * | 2018-01-31 | 2018-08-28 | 苏州维洛克电子科技有限公司 | A kind of high-strength polyester film and preparation method thereof |
| CN109336505A (en) * | 2018-10-31 | 2019-02-15 | 广西驰胜农业科技有限公司 | One kind is freeze proof to split mortar and preparation method thereof |
| CN109679578B (en) * | 2018-12-06 | 2022-09-06 | 书香门地集团股份有限公司 | Tough soybean meal protein adhesive and preparation method thereof |
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| CN1458959A (en) * | 2000-09-14 | 2003-11-26 | 罗姆和哈斯公司 | Method of forming toughened thermoset articles and toughened thermoset articles produced thereby |
| CN1542074A (en) * | 2003-11-04 | 2004-11-03 | 上海大学 | Modified urea-formaldehyde powder adhesive |
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| CN1458959A (en) * | 2000-09-14 | 2003-11-26 | 罗姆和哈斯公司 | Method of forming toughened thermoset articles and toughened thermoset articles produced thereby |
| CN1542074A (en) * | 2003-11-04 | 2004-11-03 | 上海大学 | Modified urea-formaldehyde powder adhesive |
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Effective date of registration: 20190617 Address after: 223500 Guannan Economic Development Zone, Lianyungang City, Jiangsu Province (No. 21 Shenzhen Road) Patentee after: Ganyan Tianhe Rubber Industry Co., Ltd. Address before: No. 16, No. five village, Xuanwu District, Nanjing, Jiangsu Province Patentee before: Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry |