CN1320053C - Process for preparing thermoplastic phenolic aldehyde resin/polypropylene coblend - Google Patents
Process for preparing thermoplastic phenolic aldehyde resin/polypropylene coblend Download PDFInfo
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- CN1320053C CN1320053C CNB200510112212XA CN200510112212A CN1320053C CN 1320053 C CN1320053 C CN 1320053C CN B200510112212X A CNB200510112212X A CN B200510112212XA CN 200510112212 A CN200510112212 A CN 200510112212A CN 1320053 C CN1320053 C CN 1320053C
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Abstract
The present invention discloses a process for preparing a thermoplastic phenolic resin/polypropylene blend. In a Banbury mixer, under the blending temperature of 190 to 200 DEG C, polypropylene, polypropylene grafted by maleic anhydride, thermoplastic phenolic resin and a curing agent are orderly added in the Banbury mixer for mixture; the thermoplastic phenolic resin generates 'in situ curing' and is dispersed into micron order particles under the function of high shear force, and the micron order particles are evenly distributed in the polypropylene to enhance the rigidity and the modulus of the polypropylene; the prepared blend can safety the requirements of engineering materials. The process has the advantages of simple production technology, good machining performance, strong applicability, etc.; A prepared thermoplastic phenolic resin/polypropylene blend can be used for civil constructions, automobile fittings, household appliances and other materials.
Description
Technical field
The present invention relates to a kind of preparation method of blend polymer, particularly the dynamical cure method is applied to the preparation method of novolac resin/polypropylene blend.
Background technology
1962, U.S. A.M.Gessler at first proposes to prepare rubber plastic blend type thermoplastic elastomer (US Patent 3 with dynamic vulcanization process, 037,954), after after the K.Fisher systematic study of U.S. Uniroyal company, the said firm developed dynamic part sulfurized EPT rubber (PP) thermoplastic elastomer (US Patent 3,758,643) in 1972.The beginning of the eighties, A.Y.Coran proposed the dynamic full vulcanization technology on the basis of summing up forefathers, by the development research of U.S. Monsanto company, make the dynamic full vulcanization EPT rubber/thermoplastic elastomer, and formally realized suitability for industrialized production with trade(brand)name Santoprene in nineteen eighty-two.The dynamic full vulcanization technology is that rubber and plastics carry out melt blending in mixing machinery, adds vulcanizing agent and other Synergist S-421 95 then, in blend rubber by after crosslinked fully, with dispersed phase distribution in plastics.Machine-shaping is convenient because this thermoplastic elastomer has, and waste material can reuse, the production efficiency height, and the characteristics such as low and high comprehensive performance that consume energy cause the great interest of people.
Nowadays studies show that the application of dynamic vulcanization technology not only can be applicable to plastics/blend rubber system, but also can be applicable to thermoplastic resin/aathermoset resin system.Chinese patent CN1425709A has been applied to dynamic vulcanization technology in the PP/ epoxy blend system, the polypropylene of selecting maleic anhydride graft is as expanding material, the tensile strength and the modulus in flexure of prepared dynamical cure polypropylene/epoxy resin blend are higher, and over-all properties is better.
People (Eur.Polym.J, vol.30, No.5 such as Wen yen Chiang, pp.573-580) studied heat-reactive phenolic resin/polypropylene blend, the heat-reactive phenolic resin that adds 1～4wt% has obviously improved intensity, particularly shock strength after in polypropylene, but that modulus increases is less.
Novolac resin is a kind of important thermosetting resin, itself is stable, uncured before, be a kind of oligopolymer, need just can be cured reaction by solidifying agent, form three dimensional structure.Novolac resin after the curing has advantage such as excellent cohesiveness, wear resistance, electrical insulating property, chemical stability, high thermal resistance, higher modulus and rigidity and at tackiness agent, light industry, aerospace, coating and electric insulating material, be used widely in fields such as advanced composite material matrix.Polypropylene is a kind of polyolefin resin of present consumption maximum, has the good mechanical performance, but its rigidity and modulus are not high, is difficult to satisfy the requirement of engineering materials.In order to improve polyacrylic rigidity and modulus, add mineral filler and glass fibre etc. usually therein.
Summary of the invention
The objective of the invention is dynamic vulcanization technology is applied in novolac resin/polypropylene, propose a kind of novel method of Reinforced Polypropylene.It is simple that this method has production technique, good processability, advantage such as suitability is strong.Polypropylene with maleic anhydride graft of active group can promote novolac resin and polyacrylic consistency, after adding solidifying agent, because under the effect of high shear force, " solidifying on the spot " takes place and is dispersed into micron particles in novolac resin, be evenly distributed in the polypropylene, greatly improved polyacrylic rigidity and modulus.
The preparation method of a kind of novolac resin/polypropylene blend of the present invention is as follows:
In Banbury mixer, under 190～200 ℃ blending temperature, the polypropylene, novolac resin, the solidifying agent that add polypropylene, maleic anhydride graft successively carry out mixing, wherein the polypropylene consumption is 40～85 weight parts, the consumption of maleic anhydride inoculated polypropylene is 3～15 weight parts, and the novolac resin consumption is 5～50 weight parts, and hardener dose is 0.4～8 weight part, the blend time is 7～15 minutes, obtains a kind of novolac resin/polypropylene blend.
The thermoplasticity line style resin that the novolac resin that uses among the present invention forms as phenol and formaldehyde condensation polymer or through cashew nut oil modified novolac resin.
The polypropylene that the present invention uses is homopolymer, and melting index is 2～5g/10min
The percentage of grafting of the maleic anhydride inoculated polypropylene that the present invention uses is 0.8～1%.
The solidifying agent that the present invention uses is hexamethylenetetramine, hexamethoxy methyl cyanuramide, Paraformaldehyde 96, many methylols cyanamid dimerization or many methylol dicyandiamides.
A kind of novolac resin/polypropylene blend that the present invention makes, stable performance, suitability is strong, can satisfy the requirement of engineering materials, can be used as materials such as civil construction, auto parts machinery, household electrical appliance.Preparation method provided by the present invention is easy to operate, and technology is simple, and excellent industrial application foreground is arranged.The tensile strength of material that the present invention makes, flexural strength and modulus in flexure are higher, and over-all properties is better.Compare with the mechanical property of the heat-reactive phenolic resin/PP blend of people such as Wen yen Chiang research, strength and stiffness improve more.Compare with the mechanical property of the dynamical cure Resins, epoxy/polypropylene blend that makes among the Chinese patent CN1425709A, when the amount that adds novolac resin and Resins, epoxy were all 10 weight parts, the shock strength of dynamical cure novolac resin/PP had improved 70% than the shock strength of dynamical cure Resins, epoxy/PP blend.When the amount of the novolac resin that adds and Resins, epoxy are all 30 weight parts, the tensile strength and the modulus in flexure of dynamical cure novolac resin/PP blend have improved 31% and 14% respectively, and other performance and dynamical cure Resins, epoxy/PP blend is similar.
Embodiment:
Following embodiment is to further specify of the present invention, rather than limits the scope of the invention.
Embodiment 1-7
By the prescription in the table-1, under 190 ℃ temperature, in Banbury mixer, add polypropylene (PP, the trade mark: F401, melting index 2.3g/10min successively, Liaoning Panjin petrochemical iy produced), maleic anhydride inoculated polypropylene (MAH-g-PP, percentage of grafting 1%, Shanghai day rise plastics company limited), (phenol and formaldehyde condensation polymer form thermoplasticity line style resin, the trade mark: PF-1 to novolac resin, Shanghai Qinan Adhesive Material Factory), hexamethylenetetramine (HMTA), the blend time is 10 minutes.The blend that makes is in blocks with the vulcanizing press mold pressing.Tailor batten by standard size, sample is pressed ASTM D638 respectively, ASTM D790, performance index such as ASTM D256 standard testing stretching, bending, impact.Test result is shown in table-1
Comparative Examples 1-2
What adopt is among the Chinese patent CN1425709A, the example 2 and 4 of table-1, and polyacrylic mechanical property is similar to the Properties of Polypropylene in this patent in this patent.By more as can be seen, when the amount that adds novolac resin and Resins, epoxy were all 10 weight parts, the shock strength of dynamical cure novolac resin/PP had improved 70% than the shock strength of dynamical cure Resins, epoxy/PP blend.When the amount of the novolac resin that adds and Resins, epoxy are all 30 weight parts, the tensile strength and the modulus in flexure of dynamical cure novolac resin/PP blend have improved 31% and 14% respectively, and other performance and dynamical cure Resins, epoxy/PP blend is similar.
Table-1
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative Examples 1 | Comparative Examples 2 |
| Prescription (weight fraction) PP MAH-g-PP novolac resin HMTA Resins, epoxy (DGEBA) 2-ethyl-4-methylimidazole physical and mechanical properties shock strength, the J/m tensile strength, the MPa elongation at break, the % flexural strength, the MPa modulus in flexure, MPa | 100 30.0 33.0 230 43.7 1210 | 85 10 5 0.5 48.3 35.9 13.6 56.8 1742 | 80 10 10 1.0 61.3 37.0 11.0 59.6 1783 | 70 10 20 2.0 48.5 38.3 8.9 63.4 1844 | 60 10 30 3.0 45.0 43.4 4.6 70.5 2284 | 50 10 40 4.0 29.3 36.8 4.1 63.1 2393 | 40 10 50 5.0 26.0 36.5 1.9 61.5 2451 | 80 10 10 0.4 36.0 35.0 6.9 1808 | 60 10 30 1.2 42.0 33.1 3.6 2003 |
Embodiment 10-16
By the prescription in the table-2, under 190 ℃ temperature, in Banbury mixer, add polypropylene (PP, the trade mark: F401, melting index 2.3g/10min successively, Liaoning Panjin petrochemical iy produced), the polypropylene (MAH-g-PP of maleic anhydride graft, percentage of grafting 1%, Shanghai day rise plastics company limited), novolac resin (cashew nut oil modified novolac resin, the trade mark: 2183, Shanghai Qinan Adhesive Material Factory), hexamethylenetetramine (HMTA), the blend time is 10 minutes.Specimen preparation and testing standard are operated by embodiment 1-7.Test result is shown in table-2.
Table-2
| Embodiment/project | 8 | 9 | 10 | 11 | 12 | 13 | 14 |
| Prescription (weight fraction) PP MAH-g-PP novolac resin HMTA physical and mechanical properties shock strength, the J/m tensile strength, the MPa elongation at break, the % flexural strength, the MPa modulus in flexure, MPa | 100 30.0 33.0 230 43.7 1210 | 85 10 5 0.5 35.3 34.7 14.3 52.2 1526 | 80 10 10 1.0 34.5 35.6 16.2 57.8 1703 | 70 10 20 2.0 35.5 36.4 12.9 58.1 1808 | 60 10 30 3.0 38.5 35.9 8.6 60.9 1951 | 50 10 40 4.0 34.3 36.4 6.0 62.9 2132 | 40 10 50 5.0 35.0 38.5 6.8 71.9 2588 |
Embodiment in the table-2 compares with 2 with the Comparative Examples of showing in-1 1 equally, as can be seen the similar mechanical of the two.
Claims (5)
1. the preparation method of a novolac resin/polypropylene blend, it is characterized in that the preparation method is as follows: in Banbury mixer, under 190～200 ℃ blending temperature, add polypropylene successively, the polypropylene of maleic anhydride graft, novolac resin, solidifying agent carries out mixing, wherein the polypropylene consumption is 40～85 weight parts, the polyacrylic consumption of maleic anhydride graft is 3～15 weight parts, the novolac resin consumption is 5～50 weight parts, hardener dose is 0.4～8 weight part, the blend time is 7～15 minutes, obtains a kind of novolac resin/polypropylene blend.
2. according to the described a kind of novolac resin of claim 1/polypropylene blend preparation method, it is characterized in that polypropylene is a homopolymer, melting index is 2～5g/10min.
3. according to the described a kind of novolac resin of claim 1/polypropylene blend preparation method, it is characterized in that novolac resin is that phenol and formaldehyde condensation polymer form thermoplasticity line style resin or through cashew nut oil modified novolac resin.
4. according to the described a kind of novolac resin of claim 1/polypropylene blend preparation method, the percentage of grafting that it is characterized in that maleic anhydride inoculated polypropylene is 0.8～1%.
5. according to the described a kind of novolac resin of claim 1/polypropylene blend preparation method, it is characterized in that solidifying agent is hexamethylenetetramine, hexamethoxy methyl cyanuramide, Paraformaldehyde 96, many methylols cyanamid dimerization or many methylol dicyandiamides.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB200510112212XA CN1320053C (en) | 2005-12-29 | 2005-12-29 | Process for preparing thermoplastic phenolic aldehyde resin/polypropylene coblend |
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| CNB200510112212XA CN1320053C (en) | 2005-12-29 | 2005-12-29 | Process for preparing thermoplastic phenolic aldehyde resin/polypropylene coblend |
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| CN1320053C true CN1320053C (en) | 2007-06-06 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103694558B (en) * | 2013-12-06 | 2015-09-30 | 黑龙江大学 | A kind of Phenolic aldehyde sphere/polypropylenecomposite composite material and preparation method thereof |
| CN103756144A (en) * | 2014-01-07 | 2014-04-30 | 合肥杰事杰新材料股份有限公司 | Low-linear expansion scratch-resistant highlight polypropylene composite material |
| CN106117733B (en) * | 2016-07-02 | 2018-06-05 | 天鸿建设集团有限公司 | High-strength TGXG and preparation method thereof |
| CN109721821A (en) * | 2017-10-31 | 2019-05-07 | 浙江致诚日用品有限公司 | A kind of production method of luminous plastics folder |
| CN114196114B (en) * | 2021-12-31 | 2022-11-01 | 台州市盛尔达塑业有限公司 | Novel flowerpot material and preparation method thereof |
| CN117384562B (en) * | 2023-09-28 | 2024-04-09 | 湖北慧狮塑业股份有限公司 | Solar cell electrode adhesive film and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04239542A (en) * | 1991-01-23 | 1992-08-27 | Toyoda Gosei Co Ltd | Polypropylene resin composition |
| CN1425709A (en) * | 2002-12-19 | 2003-06-25 | 上海交通大学 | Process for preparing dynamic cured epoxy resin/polypropylene blend |
-
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- 2005-12-29 CN CNB200510112212XA patent/CN1320053C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04239542A (en) * | 1991-01-23 | 1992-08-27 | Toyoda Gosei Co Ltd | Polypropylene resin composition |
| CN1425709A (en) * | 2002-12-19 | 2003-06-25 | 上海交通大学 | Process for preparing dynamic cured epoxy resin/polypropylene blend |
Non-Patent Citations (2)
| Title |
|---|
| modification of polypropylene, blending with resole typephenol-formaldehyde resins WEN.YEN CHANG,Eur.Polym.J.,Vol.第30卷 No.第5期 1994 * |
| 聚丙烯塑料增容共混改性的研究 夏正清，塑料工业，第4期 1988 * |
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Effective date of registration: 20081107 Address after: No. 1279, Lane 2, Zhongshan West Road, Shanghai Patentee after: Changning Rubber Products Factory, Shanghai Address before: No. 800, Dongchuan Road, Shanghai, Minhang District Patentee before: Shanghai Jiao Tong University |