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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Abstract
The invention provides a method for preparing an unsaturated carboxylic acid grafted polypropylene copolymer, which includes the steps: dissolving 45-300 parts by weight of unsaturated carboxylic acid grafting monomers into 280 parts by weight of N, N-dimethyl formamide, dissolving 100 parts by weight of dibenzoyl peroxide into 770 parts by weight of dimethylbenzene, mixing the solutions with 300 parts by weight of polypropylene granules and 45-700 parts by weight of styrene, mixing the mixture for one hour at the room temperature in the N2 (nitrogen) atmosphere, and carrying out a reaction for 0.5-2 hours at the temperature of 100-130 DEG C to obtain a product. The method is simple in process, free of environmental pollution and easy in aftertreatment, and grafted polypropylene containing amino acid residues has excellent biocompatibility.
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 (7)
| 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 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 |
| 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 |
| 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 |
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2012
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Patent Citations (1)
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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 |
Non-Patent Citations (1)
| Title |
|---|
| 姚瑜等: "双单体固相接枝制备亲水性PP", 《现代塑料加工应用》, vol. 17, no. 3, 30 June 2005 (2005-06-30), pages 1 - 4 * |
Cited By (13)
| 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 rate of polyolefin-grafted unsaturated carboxylic acid monomer |
| CN103897106B (en) * | 2014-03-28 | 2016-06-29 | 哈尔滨工程大学 | The method improving polyolefin graft unsaturated carboxylic acid monomer percent grafting |
| 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 |
| 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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