CN102603982A - Method for preparing unsaturated carboxylic acid grafted polypropylene copolymer - Google Patents
Method for preparing unsaturated carboxylic acid grafted polypropylene copolymer Download PDFInfo
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- CN102603982A CN102603982A CN2012100661645A CN201210066164A CN102603982A CN 102603982 A CN102603982 A CN 102603982A CN 2012100661645 A CN2012100661645 A CN 2012100661645A CN 201210066164 A CN201210066164 A CN 201210066164A CN 102603982 A CN102603982 A CN 102603982A
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 18
- 229920005606 polypropylene copolymer Polymers 0.000 title claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 43
- 239000004743 Polypropylene Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000002277 benzylpenicilloyl group Chemical group C(=O)(O)[C@@H]1N[C@H](SC1(C)C)[C@@H](C(=O)*)NC(CC1=CC=CC=C1)=O 0.000 claims description 11
- BPMFZUMJYQTVII-UHFFFAOYSA-N guanidinoacetic acid Chemical compound NC(=N)NCC(O)=O BPMFZUMJYQTVII-UHFFFAOYSA-N 0.000 claims description 8
- 150000001413 amino acids Chemical class 0.000 claims description 6
- PPRBGMXQDAMDAB-UHFFFAOYSA-N 2-(prop-2-enoylamino)propanoic acid Chemical compound OC(=O)C(C)NC(=O)C=C PPRBGMXQDAMDAB-UHFFFAOYSA-N 0.000 claims description 4
- UHWCAAMSQLMQKV-UHFFFAOYSA-N 3-methyl-2-(prop-2-enoylamino)butanoic acid Chemical compound CC(C)C(C(O)=O)NC(=O)C=C UHWCAAMSQLMQKV-UHFFFAOYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 3
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 3
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims description 3
- 235000013905 glycine and its sodium salt Nutrition 0.000 claims description 3
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 abstract description 13
- -1 Polypropylene Polymers 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 abstract 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract 1
- 125000000539 amino acid group Chemical group 0.000 abstract 1
- 239000012299 nitrogen atmosphere Substances 0.000 abstract 1
- 239000008096 xylene Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000007790 solid phase Substances 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000207 volumetry Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
本发明提供的是一种制备不饱和羧酸接枝聚丙烯共聚物的方法。分别将按重量45-300份的不饱和羧酸接枝单体溶于280份N，N-二甲基甲酰胺、100份过氧化二苯甲酰溶于770份二甲苯，再与300份聚丙烯颗粒、45-700份苯乙烯混合，N2气氛下于室温搅拌1小时，100-130℃反应0.5-2小时得到产物。本发明反应工艺简单、无环境污染、后处理容易，所得接枝聚丙烯因含有氨基酸残基而具有良好的生物相容性。The invention provides a method for preparing unsaturated carboxylic acid grafted polypropylene copolymer. Dissolve the unsaturated carboxylic acid grafting monomer of 45-300 parts by weight in 280 parts of N, N-dimethylformamide, 100 parts of dibenzoyl peroxide in 770 parts of xylene, and then with 300 parts Polypropylene particles and 45-700 parts of styrene are mixed, stirred at room temperature for 1 hour under N2 atmosphere, and reacted at 100-130° C. for 0.5-2 hours to obtain the product. The invention has the advantages of simple reaction process, no environmental pollution and easy post-treatment, and the obtained grafted polypropylene has good biocompatibility because of containing amino acid residues.
Description
Technical field
That the present invention relates to is a kind of preparation method of organic high molecular polymer, specifically a kind of polypropylene grafted method of modifying.
Background technology
Vestolen PP 7052 has fusing point height, good heat resistance, density is little, mechanical property is excellent and good chemical stability, is widely used in fields such as wrapping material, component of machine, household electrical appliance, medicine equipment, synthon.In the nearest 20 years time, Vestolen PP 7052 continues the fastest tempo of maintenance in general-purpose plastics.
Although Vestolen PP 7052 has numerous advantages,, the Vestolen PP 7052 part that also comes with some shortcomings.Disadvantage is that winter hardiness is poor, and is fragile under low temperature disconnected; Next is that shrinking percentage is big, and creep resistance is poor, and the product size poor stability is easy to generate buckling deformation; Compare with traditional engineering plastics, Vestolen PP 7052 also exists weathering resistance poor, fast light, heat-resisting and resistance to deterioration is poor, and is hydrophilic and antistatic property is poor, covers with paint, lacquer, colour wash, etc., suitability for secondary processing such as painted and bonding is poor, and is poor with the consistency of other polymkeric substance and mineral filler.Thereby limited polyacrylic further application.In order to improve its performance, improve its range of application, need Vestolen PP 7052 is carried out modification.
Polyacrylic grafting modification method has: solution grafting, fusion-grafting method and solid phase grafting method etc.Wherein preceding two kinds of methods need reaction at high temperature, and polypropylene molecular chain is easy to chain rupture takes place and degrades, and this makes that polyacrylic performance significantly decreases after the graft modification.Solid phase grafting is a kind of graft-modification method that rises the nineties in 20th century; Compare with other grafting methods; Advantage such as the versatility that it has temperature of reaction low (be generally 90～120 ℃, be lower than the fusing point of polymkeric substance), working pressure low (being generally normal pressure), conversion unit is big, side reaction is less, solvent-free pollution, aftertreatment are simple.But also there are some shortcomings in the solid phase grafting method, is difficult to the percentage of grafting that reaches high like the solid phase grafting method, and occurs material in the reaction process easily and be bonded to phenomenons such as piece, stirring and heat transfer be inhomogeneous.Through introducing suitable auxiliary grafted monomer, not only can effectively stop the degraded side reaction of Vestolen PP 7052 in the grafting process, also help to improve the percentage of grafting of product.
Vestolen PP 7052 solid phase grafting monomer commonly used at present mainly contains maleic anhydride, SY-Monomer G, vinylformic acid, methylacrylic acid, TEB 3K etc.; These monomers often all have bigger toxicity; And boiling point is low; Volatile or distillation brings grievous injury to site operation personnel's eyes and skin, brings difficulty to actual production.
Summary of the invention
The object of the present invention is to provide that a kind of reaction process is simple, non-environmental-pollution, aftertreatment be easy, can access the method for preparing the unsaturated carboxylic acid graft polypropylene copolymer of the graft polypropylene with excellent biological compatibility.
The objective of the invention is to realize like this:
The unsaturated carboxylic acid graft monomer of 45-300 part is dissolved in 280 parts of N by weight respectively, and dinethylformamide, 100 parts of BPOs are dissolved in 770 parts of YLENE, mix N again with 300 parts of PP GRANULESs, 45-700 part vinylbenzene
2In stirring at room 1 hour, 100-130 ℃ of reaction obtained product in 0.5-2 hour under the atmosphere.
The present invention can also comprise:
Described unsaturated carboxylic acid graft monomer is under alkaline condition, to react resulting grafted monomer through acrylate chloride and amino acid, and the general formula that reacts is expressed as:
Said amino acid is proline(Pro), glycocoll, L-Ala, Xie Ansuan, and pairing unsaturated carboxylic acid graft monomer is respectively 1-acryloyl tetramethyleneimine-2-carboxylic acid, 2-acrylic amide guanidine-acetic acid, 2-acrylamido propionic acid, 2-acrylamido-3 Methylbutanoic acid.
Preferred 30: 70 to 70: 30 of unsaturated carboxylic acid graft monomer and cinnamic weight ratio.
The reaction unit that the present invention adopted is for having condensing works, magnetic stirring apparatus, N
2The capping system of tightness system and charging opening.
In order to obtain purified graft product; The present invention washs graft product with methyl alcohol and acetone respectively; Purpose is to remove unsaturated carboxylic acid and cinnamic homopolymer, multipolymer and unreacted monomer and other auxiliary agents, again through vacuum-drying, can obtain final graft product.
Compared with prior art, the present invention has following characteristic:
1) first several kinds of above-mentioned solid unsaturated carboxylic acids is applied to polypropylene grafted modification, has prepared the novel polypropylene graft copolymer of high percentage of grafting;
2) because institute's synthetic unsaturated carboxylic acid monomer is not soluble in interfacial agents YLENE, and the present invention is dissolved in N earlier with monomer, in the dinethylformamide, and the initiator BPO still is dissolved in the YLENE.
3) because polypropylene grafted method of modifying of the present invention belongs to radical reaction mechanism, oxygen is very big for the influence of reaction in the air, so the reaction unit that the present invention adopts is for having condensing works, magnetic stirring apparatus, N
2The capping system of tightness system and charging opening.
4) the present invention have that reaction process is simple, non-environmental-pollution, advantage such as temperature of reaction is lower, working pressure is low and aftertreatment is simple, can obtain the novel polypropylene graft copolymer of higher percentage of grafting simultaneously.
Description of drawings
Fig. 1 is the infrared spectrogram of Vestolen PP 7052 and polypropylene grafted product.Curve a is polyacrylic infrared spectrogram among the figure, and curve b is the infrared spectrogram of polypropylene grafted unsaturated carboxylic acid monomer.Visible by Fig. 1, the graft product infrared spectrum is at 1723cm
-1And 1602cm
-1The carbonyl absorption peak of acid amides and carboxylic acid has appearred belonging to respectively, at 699cm
-1Cinnamic absorption peak occurred belonging to, therefore can judge that unsaturated carboxylic acid graft monomer and vinylbenzene successfully are grafted on the polyacrylic molecular chain.
Embodiment
Basic skills of the present invention comprises
(1) through acrylate chloride and the prepared in reaction grafted monomer of corresponding amino acid under alkaline condition;
(2) inciting somebody to action by weight respectively, the unsaturated carboxylic acid graft monomer of 45-300 part is dissolved in 280 parts of N; Dinethylformamide, 100 parts of initiator BPOs are dissolved in 770 parts of interfacial agents YLENE; Mix N with 300 parts of PP GRANULESs, the auxiliary grafted monomer vinylbenzene of 45-700 part again
2Under room temperature, stirred 1 hour under the atmosphere, 100-130 ℃ was reacted 0.5-2 hour, can obtain the polypropylene grafted product of high percentage of grafting, through cooling, filtration, washing and drying, promptly obtained final graft product again.
The amino acid of when preparation unsaturated carboxylic acid graft monomer, selecting for use comprises proline(Pro), glycocoll, L-Ala and Xie Ansuan, and corresponding unsaturated carboxylic acid graft monomer is respectively 1-acryloyl tetramethyleneimine-2-carboxylic acid, 2-acrylic amide guanidine-acetic acid, 2-acrylamido propionic acid and 2-acrylamido-3 Methylbutanoic acid.
The unsaturated carboxylic acid graft monomer and the cinnamic weight ratio of auxiliary grafted monomer that adopt are 10: 90 to 90: 10, preferred 30: 70 to 70: 30.
The reaction unit that adopts is for having condensing works, magnetic stirring apparatus, N
2The capping system of tightness system and charging opening.
Below in conjunction with embodiment the present invention is made further detailed description.
Embodiment 1:
Unsaturated carboxylic acid graft monomer 1-acryloyl tetramethyleneimine-2-carboxylic acid of 300 parts is dissolved in 280 parts of N by weight respectively, and dinethylformamide, 100 parts of initiator BPOs are dissolved in 770 parts of interfacial agents YLENE, in N
2Under the atmosphere two kinds of solution are joined and be equipped with in 300 parts of COPP particles and the 700 parts of cinnamic reaction units of auxiliary grafted monomer.React 30min down at 110 ± 2 ℃, cooling is filtered, and uses methyl alcohol and washing with acetone respectively, and vacuum-drying promptly obtains final graft product, and its percentage of grafting is 14.3%.
The percentage of grafting measuring method of unsaturated carboxylic acid is a volumetry in the graft product of modified polypropene, and concrete grammar is following: at first graft product was used acetone and methyl alcohol extracting respectively 24 hours, with remove maybe be residual vinylbenzene and unsaturated carboxylic acid homopolymer.Accurately take by weighing the graft product of a certain amount of (m), be dissolved in the 50mL YLENE, adding excessive concentration is C
1KOH-ethanol standardized solution V
1ML is in 110 ℃ of refluxed 1hr.After question response is abundant, be C with concentration
2Acetate-YLENE standardized solution return and drip an excess base, the consumption volume is V
2ML is calculated as follows out percentage of grafting (at every turn measuring parallel three times):
In the formula, M is the molar mass of unsaturated carboxylic acid monomer.
Can know that through calculating the percentage of grafting of this comparative example graft product unsaturated carboxylic acid is 14.3%.
Embodiment 2:
Unsaturated carboxylic acid graft monomer 1-acryloyl tetramethyleneimine-2-carboxylic acid of 150 parts is dissolved in 280 parts of N by weight respectively, and dinethylformamide, 100 parts of initiator BPOs are dissolved in 770 parts of interfacial agents YLENE, in N
2Under the atmosphere two kinds of solution are joined and be equipped with in 300 parts of COPP particles and the 350 parts of cinnamic reaction units of auxiliary grafted monomer.React 30min down at 110 ± 2 ℃, cooling is filtered, and uses methyl alcohol and washing with acetone respectively, and vacuum-drying promptly obtains final graft product, and its percentage of grafting is 6.7%.
Embodiment 3:
Unsaturated carboxylic acid graft monomer 1-acryloyl tetramethyleneimine-2-carboxylic acid of 45 parts is dissolved in 280 parts of N by weight respectively, and dinethylformamide, 100 parts of initiator BPOs are dissolved in 770 parts of interfacial agents YLENE, in N
2Under the atmosphere two kinds of solution are joined and be equipped with in 300 parts of COPP particles and the 105 parts of cinnamic reaction units of auxiliary grafted monomer.React 30min down at 110 ± 2 ℃, cooling is filtered, and uses methyl alcohol and washing with acetone respectively, and vacuum-drying promptly obtains final graft product, and its percentage of grafting is 5.1%.
Embodiment 4:
Unsaturated carboxylic acid graft monomer 1-acryloyl tetramethyleneimine-2-carboxylic acid of 75 parts is dissolved in 280 parts of N by weight respectively, and dinethylformamide, 100 parts of initiator BPOs are dissolved in 770 parts of interfacial agents YLENE, in N
2Under the atmosphere two kinds of solution are joined and be equipped with in 300 parts of COPP particles and the 75 parts of cinnamic reaction units of auxiliary grafted monomer.React 30min down at 110 ± 2 ℃, cooling is filtered, and uses methyl alcohol and washing with acetone respectively, and vacuum-drying promptly obtains final graft product, and its percentage of grafting is 3.8%.
Embodiment 5:
Unsaturated carboxylic acid graft monomer 1-acryloyl tetramethyleneimine-2-carboxylic acid of 105 parts is dissolved in 280 parts of N by weight respectively, and dinethylformamide, 100 parts of initiator BPOs are dissolved in 770 parts of interfacial agents YLENE, in N
2Under the atmosphere two kinds of solution are joined and be equipped with in 300 parts of COPP particles and the 45 parts of cinnamic reaction units of auxiliary grafted monomer.React 30min down at 110 ± 2 ℃, cooling is filtered, and uses methyl alcohol and washing with acetone respectively, and vacuum-drying promptly obtains final graft product, and its percentage of grafting is 2.8%.
Embodiment 6:
45 parts unsaturated carboxylic acid graft monomer 2-acrylic amide guanidine-acetic acid is dissolved in 280 parts of N by weight respectively, and dinethylformamide, 100 parts of initiator BPOs are dissolved in 770 parts of interfacial agents YLENE, in N
2Under the atmosphere two kinds of solution are joined and be equipped with in 300 parts of COPP particles and the 105 parts of cinnamic reaction units of auxiliary grafted monomer.React 30min down at 110 ± 2 ℃, cooling is filtered, and uses methyl alcohol and washing with acetone respectively, and vacuum-drying promptly obtains final graft product, and its percentage of grafting is 3.2%.
Embodiment 7:
45 parts unsaturated carboxylic acid graft monomer 2-acrylamido propionic acid is dissolved in 280 parts of N by weight respectively, and dinethylformamide, 100 parts of initiator BPOs are dissolved in 770 parts of interfacial agents YLENE, in N
2Under the atmosphere two kinds of solution are joined and be equipped with in 300 parts of COPP particles and the 105 parts of cinnamic reaction units of auxiliary grafted monomer.React 30min down at 110 ± 2 ℃, cooling is filtered, and uses methyl alcohol and washing with acetone respectively, and vacuum-drying promptly obtains final graft product, and its percentage of grafting is 4.9%.
Embodiment 8:
Unsaturated carboxylic acid graft monomer 2-acrylamido-3 Methylbutanoic acid of 45 parts is dissolved in 280 parts of N by weight respectively, and dinethylformamide, 100 parts of initiator BPOs are dissolved in 770 parts of interfacial agents YLENE, in N
2Under the atmosphere two kinds of solution are joined and be equipped with in 300 parts of COPP particles and the 105 parts of cinnamic reaction units of auxiliary grafted monomer.React 30min down at 110 ± 2 ℃, cooling is filtered, and uses methyl alcohol and washing with acetone respectively, and vacuum-drying promptly obtains final graft product, and its percentage of grafting is 4.3%.
Claims (4)
1. method for preparing the unsaturated carboxylic acid graft polypropylene copolymer; It is characterized in that: the unsaturated carboxylic acid graft monomer of 45-300 part is dissolved in 280 parts of N by weight respectively; Dinethylformamide, 100 parts of BPOs are dissolved in 770 parts of YLENE; Mix N with 300 parts of PP GRANULESs, 45-700 part vinylbenzene again
2In stirring at room 1 hour, 100-130 ℃ of reaction obtained product in 0.5-2 hour under the atmosphere.
2. a kind of method for preparing the unsaturated carboxylic acid graft polypropylene copolymer according to claim 1; It is characterized in that: described unsaturated carboxylic acid graft monomer is under alkaline condition, to react resulting grafted monomer through acrylate chloride and amino acid, and the general formula that reacts is expressed as:
3. a kind of method for preparing the unsaturated carboxylic acid graft polypropylene copolymer according to claim 2; It is characterized in that: said amino acid is proline(Pro), glycocoll, L-Ala, Xie Ansuan, and pairing unsaturated carboxylic acid graft monomer is respectively 1-acryloyl tetramethyleneimine-2-carboxylic acid, 2-acrylic amide guanidine-acetic acid, 2-acrylamido propionic acid, 2-acrylamido-3 Methylbutanoic acid.
4. according to claim 1,2 or 3 described a kind of methods that prepare the unsaturated carboxylic acid graft polypropylene copolymer, it is characterized in that: preferred 30: 70 to 70: 30 of unsaturated carboxylic acid graft monomer and cinnamic weight ratio.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911316A (en) * | 2012-10-29 | 2013-02-06 | 哈尔滨工程大学 | Method for grafting polar monomer onto polypropylene through aqueous suspension solid-phase graft |
| CN103224593A (en) * | 2013-04-16 | 2013-07-31 | 哈尔滨工程大学 | Method for grafting linear low density polyethylene to polar monomer |
| CN103232575A (en) * | 2013-04-11 | 2013-08-07 | 哈尔滨工程大学 | Preparation method for solid unsaturated carboxylic acid-functionalized linear low density polyethylene |
| CN103897106A (en) * | 2014-03-28 | 2014-07-02 | 哈尔滨工程大学 | Method for Improving Grafting Ratio of Polyolefin Grafted Unsaturated Carboxylic Acid Monomer |
| CN105837741A (en) * | 2016-05-14 | 2016-08-10 | 上海大学 | Oligomeric proline methyl acrylate/dimethyl ammonium ethyl methyl methacrylate copolymer and preparation method thereof |
| CN111334265A (en) * | 2020-04-13 | 2020-06-26 | 西南石油大学 | Clay mineral nano hydrogel plugging agent and water-based drilling fluid |
| CN116377652A (en) * | 2023-04-18 | 2023-07-04 | 浙江京博聚烯烃新材料有限公司 | A kind of hydrophilic modified polypropylene non-woven fabric and its preparation method and application |
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| CN1283642A (en) * | 2000-08-30 | 2001-02-14 | 华南理工大学 | Process for preparing soild-phase graft copolymer of polyolefine and three monomers and its application |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911316A (en) * | 2012-10-29 | 2013-02-06 | 哈尔滨工程大学 | Method for grafting polar monomer onto polypropylene through aqueous suspension solid-phase graft |
| CN102911316B (en) * | 2012-10-29 | 2015-03-11 | 哈尔滨工程大学 | Method for grafting polar monomer onto polypropylene through aqueous suspension solid-phase graft |
| CN103232575A (en) * | 2013-04-11 | 2013-08-07 | 哈尔滨工程大学 | Preparation method for solid unsaturated carboxylic acid-functionalized linear low density polyethylene |
| CN103232575B (en) * | 2013-04-11 | 2015-05-27 | 哈尔滨工程大学 | Preparation method for solid unsaturated carboxylic acid-functionalized linear low density polyethylene |
| CN103224593B (en) * | 2013-04-16 | 2015-12-09 | 哈尔滨工程大学 | A kind of method of linear low density polyethylene grafting of polar monomers |
| CN103224593A (en) * | 2013-04-16 | 2013-07-31 | 哈尔滨工程大学 | Method for grafting linear low density polyethylene to polar monomer |
| CN103897106A (en) * | 2014-03-28 | 2014-07-02 | 哈尔滨工程大学 | Method for Improving Grafting Ratio of Polyolefin Grafted Unsaturated Carboxylic Acid Monomer |
| CN103897106B (en) * | 2014-03-28 | 2016-06-29 | 哈尔滨工程大学 | Method for improving grafting rate of polyolefin grafted unsaturated carboxylic acid monomer |
| CN105837741A (en) * | 2016-05-14 | 2016-08-10 | 上海大学 | Oligomeric proline methyl acrylate/dimethyl ammonium ethyl methyl methacrylate copolymer and preparation method thereof |
| CN105837741B (en) * | 2016-05-14 | 2018-01-02 | 上海大学 | Oligomerization proline methacrylate/dimethylaminoethyl methacrylate copolymer and preparation method thereof |
| CN111334265A (en) * | 2020-04-13 | 2020-06-26 | 西南石油大学 | Clay mineral nano hydrogel plugging agent and water-based drilling fluid |
| CN116377652A (en) * | 2023-04-18 | 2023-07-04 | 浙江京博聚烯烃新材料有限公司 | A kind of hydrophilic modified polypropylene non-woven fabric and its preparation method and application |
| CN117457290A (en) * | 2023-11-01 | 2024-01-26 | 佛山市粤佳信电线电缆有限公司 | High-flexibility drag chain cable and forming process thereof |
| CN117457290B (en) * | 2023-11-01 | 2024-04-16 | 佛山市粤佳信电线电缆有限公司 | High-flexibility drag chain cable and forming process thereof |
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