CN103724935A - Method for performing toughening modification on urea resin - Google Patents
Method for performing toughening modification on urea resin Download PDFInfo
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- CN103724935A CN103724935A CN201310745020.7A CN201310745020A CN103724935A CN 103724935 A CN103724935 A CN 103724935A CN 201310745020 A CN201310745020 A CN 201310745020A CN 103724935 A CN103724935 A CN 103724935A
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Abstract
The invention discloses a method for performing toughening modification on a urea resin. The method comprises the following steps: uniformly mixing toughening agents such as acrylic polymers, vinyl polymers or acetal polymers and the urea resin through dispersing equipment to obtain urea resin molding powder, wherein the ratio of the toughening agents such as acrylic polymers, vinyl polymers or acetal polymers which account for the mass of the mixture does not exceed 80 percent; pressing the urea resin molding powder with the granularity of 60-200 meshes under the conditions of 80-200 DEG C and 5-60MPa for 2-20 minutes by using a press vulcanizer, and preparing impact splines or bending splines. The urea resin is subjected to toughening modification by using the self-made toughening agents such as acrylic polymers or commercially available vinyl polymers or acetal polymers, wherein the self-made toughening agents such as acrylic polymers have the best toughening effect, the impact strength is 2.50kJ/m<2>, and the bending strength is 85MPa.
Description
Technical field
The present invention relates to the method for toughening of aminoresin molding powder, the acrylic polymer of specifically preparing with oneself or the method for vinylic polymers or acetals polymer toughening urea-formaldehyde resin.
Background technology
Urea-formaldehyde resin moulding material is the insoluble not molten thermosetting material of being made through operations such as plasticizing processing and compression moldings by a series of auxiliary agents 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, at aspects such as alternative common plastics, domestic ceramics, timber and metallic substance, gathers around and has great advantage.CN 101113230A provides a kind of unsaturated polyester cross-linking waste to prepare the method for 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. are pressed 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, mixed powder is carried out to compression molding, 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, the moulding compound making 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, shock strength improve be not clearly (Han Chunguo, Li Shouhai, Wang Chunpeng, etc., the impact of softening agent on urea-formaldehyde resin moulding compound performance, modern chemical industry, 2011,31(2): 61-65).The object of the invention is, when improving aminoresin toughness, to promote the Application Areas of aminoresin.
Summary of the invention
the technical problem solving:low in order to solve the urea-formaldehyde resin moulding compound intensity existing in prior art, the shortcomings such as poor toughness, the invention provides a kind of method of urea-formaldehyde resin toughening modifying, and the molding test specimen making has the advantages 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 are mixed and obtained urea-formaldehyde resin molding powder by dispersing apparatus with urea-formaldehyde resin, and 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 molding powder at 80～200 ℃, under 5～60MPa condition, suppress 2～20min, make and impact batten or crooked 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 to prepare 20%～40% of acrylic polymer water total mass, again by soft, hard monomer (1～12) in mass ratio: (20～6) are added drop-wise in pre-emulsification still in the situation that stirring, under room temperature, stir 0.5～5h and make pre-emulsion, wherein soft or hard monomer total mass used is 3/7～7/3 with the ratio of preparing acrylic polymer water total mass; Getting emulsifying agent and water is added in reactor again, in reactor, the consumption of water is to prepare 60%～80% of acrylic polymer water total mass, then get in the water that 1/20～1/10 of pre-emulsion total mass is added to this reactor, and adding initiator in remaining pre-emulsion, initiator amount is add 0.1%～5% of 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 consumption for the second time; When reactor is warming up to 50 ℃～100 ℃, the pre-emulsion that adds initiator is added drop-wise in reactor, at 2～6h, drips off, after insulation 0.5～4 h, emulsion is filtered and is obtained in cooling; The emulsion of preparation is dry at 30～80 ℃, with pulverizer, be crushed to 60～200 orders, obtain acrylic polymer toughner.
Described vinylic polymers is at least one in polystyrene, polyvinyl alcohol, vinyl-vinyl acetate copolymers, polyvinyl acetate copolymer, ethene-vinyl acetate-tertiary ethylene carbonate multipolymer.
Described acetals polymkeric substance be polyvinyl formal, polyvinylacetal, polyvinyl formal acetal, polyvinyl butyral acetal, vinyl acetals polymkeric substance, contracting oxalic dialdehyde, at least one in cardanol aminal, acetal urushiol amine, 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.
At least one in the polyoxyethylene phenolic ether in the ninth of the ten Heavenly Stems that described initiator is that 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 16.
Described soft monomer is at least one in n-butyl acrylate, vinylformic acid pentyl ester, 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 carries out toughening modifying with homemade toughner acrylic polymer or commercially available acetals polymkeric substance or vinylic polymers to urea-formaldehyde resin, and wherein, best with homemade acrylic polymer toughening effect, shock strength is 2.50kJ/m
2, flexural strength is 85 MPa.
Embodiment
Below in conjunction with concrete example, further illustrate the solution of the present invention and effect.
embodiment 1:
(1) pre-emulsification: in pre-emulsification still, the emulsifier mixture of 1.35g OP, 0.90 g sodium stearate and 0.25g SDS 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 water under agitation condition, churning time is 4h, makes pre-emulsion.
(2) seeded emulsion polymerization: in reactor, getting 0.35g polyoxyethylene nonylphenol ether and 0.15g sodium dibutyl naphthalene sulfonate is added in 480g water and forms water, getting 75g pre-emulsion is added in water, while being warming up to 85 ℃, will add the residue pre-emulsion of 2.50g initiator ammonium persulfate to be added drop-wise to polyreaction in reactor with 3h, emulsion is filtered and obtained to insulation after being down to room temperature after 1h.
(3) toughness reinforcing urea-formaldehyde resin: the emulsion of above-mentioned preparation is dry at 40 ℃, with pulverizer, be crushed to 140 orders and obtain acrylic ester polymer, this polymkeric substance of 20g is mixed and makes modification molding powder with kneader with 80g urea-formaldehyde resin, get 60g modification molding powder at 165 ℃, under 30MPa condition, with vulcanizing press mold pressing 10min moulding, the urea-formaldehyde resin that makes certain size impacts batten (band breach); Get 20g modification molding powder at 160 ℃, mold pressing 6min moulding under 25MPa, makes the crooked batten of modified urea-formaldehyde resin of certain size.
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 7.50g OS emulsifier mixture.75g soft monomer vinylformic acid pentyl ester and 20g vinyl cyanide, 375g β-dimethyl-aminoethylmethacrylate, 30g N methacrylamide monomer are added drop-wise in pre-emulsification still after mixing, getting 75g pre-emulsion is added in the water that contains 1.00g polyoxyethylene nonylphenol ether and 1.20g SDS, while being warming up to 95 ℃, will add the residue pre-emulsion of 3.50g initiator peroxidized t-butyl perbenzoate and 6.50g dibenzoyl peroxide to be added drop-wise to polyreaction in reactor with 5h, emulsion is filtered and obtained to insulation after being down to room temperature after 0.5h.Other formulas are identical with embodiment 1 with technique.
(2) toughness reinforcing urea-formaldehyde resin: the emulsion of above-mentioned preparation is dry at 50 ℃, with pulverizer, be crushed to 100 orders and obtain acrylic ester polymer, this polymkeric substance of 35g is mixed and makes modification molding powder with kneader with 65g urea-formaldehyde resin, get 60g modification molding powder at 120 ℃, under 40MPa condition, with vulcanizing press mold pressing 16min moulding, the urea-formaldehyde resin that makes certain size impacts batten (band breach); Get 20g modification molding powder at 115 ℃, mold pressing 7min moulding under 45MPa, makes the crooked batten of modified urea-formaldehyde resin of certain size.
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 0.40g SDS, 0.20g dehydrogenation potassium rosinate and 0.15g sodium dibutyl naphthalene sulfonate mixture.250g soft monomer vinylformic acid pentyl ester, 30g glycidyl methacrylate and 170g methyl acrylate, 50g N methacrylamide hard monomer are added drop-wise in pre-emulsification still after mixing, getting 75g pre-emulsion is added in the water containing emulsifying agent 0.10g OP and 0.15g sodium dibutyl naphthalene sulfonate, while being warming up to 55 ℃ by adding initiator 0.33g cyclohexanone peroxide, 0.28g naphthoic acid is cuprous and the residue pre-emulsion of 0.39g triethyl aluminum is added drop-wise to polyreaction in reactor with 2h, filters and obtain emulsion after being down to room temperature after insulation 3.5 h.Other formulas are identical with embodiment 1 with technique.
(2) toughness reinforcing urea-formaldehyde resin: the emulsion of above-mentioned preparation is dry at 50 ℃, with pulverizer, be crushed to 150 orders and obtain acrylic ester polymer, this polymkeric substance of 55g is mixed and makes modification molding powder with mill with 45g urea-formaldehyde resin, get 60g modification molding powder at 180 ℃, under 20MPa condition, with vulcanizing press mold pressing 8min moulding, the urea-formaldehyde resin that makes certain size impacts batten (band breach); Get 20g modification molding powder at 175 ℃, mold pressing 7min moulding under 20MPa, makes the crooked batten of modified urea-formaldehyde resin of certain size.
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 90g 120 object urea-formaldehyde resins evenly make molding powder with kneader blend.Get 60g modification molding powder at 175 ℃, under 30MPa condition, with vulcanizing press mold pressing 11min moulding, the urea-formaldehyde resin that makes certain size impacts batten (band breach); Get 20g modification molding powder at 170 ℃, mold pressing 4min moulding under 35MPa, makes the crooked batten of modified urea-formaldehyde resin of certain size.
The impact that the present embodiment prepares and crooked test batten fundamental property the results are shown in subordinate list 1.
embodiment 5:
40g vinyl-vinyl acetate copolymers and 60g 180 object urea-formaldehyde resins evenly make molding powder with Banbury mixer blend.Get 60g modification molding powder at 90 ℃, under 60MPa condition, with vulcanizing press mold pressing 18min moulding, the urea-formaldehyde resin that makes certain size impacts batten (band breach); Get 20g modification molding powder at 85 ℃, mold pressing 10min moulding under 55MPa, makes the crooked batten of modified urea-formaldehyde resin of certain size.
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 30g 80 object urea-formaldehyde resins evenly make molding powder with kneader blend.Get the molding powder that 60g mixes, get 60g modification molding powder at 140 ℃, under 55MPa condition, with vulcanizing press mold pressing 14min moulding, the urea-formaldehyde resin that makes certain size impacts batten (band breach); Get 20g modification molding powder at 135 ℃, mold pressing 5min moulding under 45MPa, makes the crooked batten of modified urea-formaldehyde resin of certain size.
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 and makes molding powder with pulverizer with 50g 120 object urea-formaldehyde resins.Get the molding powder that 60g mixes, get 60g modification molding powder at 195 ℃, under 20MPa condition, with vulcanizing press mold pressing 8min moulding, the urea-formaldehyde resin that makes certain size impacts batten (band breach); Get 20g modification molding powder at 190 ℃, mold pressing 3min moulding under 15MPa condition, makes the crooked batten of modified urea-formaldehyde resin of certain size.
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 molding of each toughner powder
Note: according to GB 13454-92, 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 qualified requirement; "-" represents that mold pressing batten can not moulding, cannot detect.
Subordinate list 1 result shows, the toughness reinforcing urea-formaldehyde resin effect of esters of acrylic acid toughner of embodiment 1 of the present invention is more excellent.
Above-mentioned flexural strength test is to use SANS CMT Series Microcomputer to control electronic universal tester (Shenzhen Sans Material Detection Co., Ltd); Test shock strength is to use XJJY-5 liquid-crystal display impact tester for simple supported beam (Chengde Xin Guo test set company limited).
Claims (7)
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 are mixed and obtained urea-formaldehyde resin molding powder by dispersing apparatus with urea-formaldehyde resin, and 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 molding powder at 80～200 ℃, under 5～60MPa condition, suppress 2～20min, make and impact batten or crooked 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 to prepare 20%～40% of acrylic polymer water total mass, again by soft, hard monomer (1～12) in mass ratio: (20～6) are added drop-wise in pre-emulsification still in the situation that stirring, under room temperature, stir 0.5～5h and make pre-emulsion, wherein soft or hard monomer total mass used is 3/7～7/3 with the ratio of preparing acrylic polymer water total mass; Getting emulsifying agent and water is added in reactor again, in reactor, the consumption of water is to prepare 60%～80% of acrylic polymer water total mass, then get in the water that 1/20～1/10 of pre-emulsion total mass is added to this reactor, and adding initiator in remaining pre-emulsion, initiator amount is add 0.1%～5% of 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 consumption for the second time; When reactor is warming up to 50 ℃～100 ℃, the pre-emulsion that adds initiator is added drop-wise in reactor, at 2～6h, drips off, after insulation 0.5～4 h, emulsion is filtered and is obtained in cooling; The emulsion of preparation is dry at 30～80 ℃, with pulverizer, be crushed to 60～200 orders, obtain acrylic polymer toughner.
2. the method for urea-formaldehyde resin toughening modifying according to claim 1, is characterized in that described vinylic polymers is at least one in polystyrene, polyvinyl alcohol, vinyl-vinyl acetate copolymers, polyvinyl acetate copolymer, ethene-vinyl acetate-tertiary ethylene carbonate multipolymer.
3. 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 acetals polymkeric substance, contracting oxalic dialdehyde, at least one in cardanol aminal, acetal urushiol amine, aromatic diacid ester acetal polymer.
4. 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.
5. the method for urea-formaldehyde resin toughening modifying according to claim 1, at least one in the polyoxyethylene phenolic ether in the ninth of the ten Heavenly Stems that it is characterized in that described initiator is that 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 is 16.
6. the method for urea-formaldehyde resin toughening modifying according to claim 1, is characterized in that described soft monomer is at least one in n-butyl acrylate, vinylformic acid pentyl ester, 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.
7. 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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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104210000A (en) * | 2014-09-11 | 2014-12-17 | 安徽农业大学 | Embrittlement-prevention treatment method for palm rattan materials |
| CN105885320A (en) * | 2016-06-13 | 2016-08-24 | 上海金山锦湖日丽塑料有限公司 | PMMA resin with ultrahigh toughness |
| 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 |
| CN109679578A (en) * | 2018-12-06 | 2019-04-26 | 书香门地（上海）美学家居股份有限公司 | A kind of toughness dregs of beans albumen adhesive and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104210000A (en) * | 2014-09-11 | 2014-12-17 | 安徽农业大学 | Embrittlement-prevention treatment method for palm rattan materials |
| CN105885320A (en) * | 2016-06-13 | 2016-08-24 | 上海金山锦湖日丽塑料有限公司 | PMMA resin with ultrahigh toughness |
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| 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 |
| CN109679578A (en) * | 2018-12-06 | 2019-04-26 | 书香门地（上海）美学家居股份有限公司 | A kind of toughness dregs of beans albumen adhesive 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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