CN102993376A - Polypropylene-hydrophilic monomer copolymer and preparation method thereof - Google Patents
Polypropylene-hydrophilic monomer copolymer and preparation method thereof Download PDFInfo
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- CN102993376A CN102993376A CN2012105477249A CN201210547724A CN102993376A CN 102993376 A CN102993376 A CN 102993376A CN 2012105477249 A CN2012105477249 A CN 2012105477249A CN 201210547724 A CN201210547724 A CN 201210547724A CN 102993376 A CN102993376 A CN 102993376A
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Abstract
The invention provides a polypropylene-hydrophilic monomer copolymer and a preparation method thereof. The copolymer is prepared by a solid-phase synthesis method through a solvent-free internal mixer. In the preparation process, polypropylene swelled with an adhesion agent, an initiator, the hydrophilic monomer and an oxidant have a graft polymerization reaction in proportion in the internal mixer to prepare the polypropylene-hydrophilic monomer copolymer. According to the preparation method, no solvent is used, the problem that the environment is polluted by solvents is solved, and the production cost is reduced; by adoption of the technical means of graft polymerization reaction in the internal mixer, the operation is easy and convenient, the used hydrophilic monomer has carbon-carbon double bonds, auto-agglutination is easily caused; and since hydrophilic groups are increased, the hydrophilic property of the polypropylene is improved.
Description
Technical field
The present invention relates to a kind of method of polypropylene hydrophilic modifying, particularly a kind of method of Solid-Phase Grafting of Methyl-Methacrylate hydrophile monomer.
Background technology
Polypropylene (PP) is one of the most widely used polymkeric substance, and current production rate is only second to the second largest resin of polyethylene (PE).The advantages such as it has with low cost, good mechanical performance, resistance toheat is good, chemical stability good, insulating property are good, but owing to do not have polar group in the molecule, wetting ability is relatively poor, has hindered it and has used more widely.In order to overcome this shortcoming, polypropylene need to be carried out hydrophilic modifying.
That the main method of polypropylene hydrophilic modifying has is polypropylene blending modified, surface treatment and body modification etc.Blend is that polypropylene modification industry common are one of effect means; the advantage such as that this kind method has is with low cost, simple to operate, the technology handiness is large; but processing condition are changeful, usually can cause the variation of system form, so that variation has also occured the performance of blend.Mostly surface treatment is the radiotreatment method, and such as plasma body, gamma-rays etc., Kim etc. such as water, vinylformic acid, allylamine, use the plasma modification microporous polypropylene membrane under different atmosphere.Result's demonstration, although the film wettability of the surface increases significantly under water and acrylic acid atmosphere (contact angle is from 100 °-40 °), the mechanical property severe exacerbation, this is because the etching that oxidation causes; In addition, under allylamine atmosphere, the surface of film has produced thin barrier film.CO is used on the surface that has in addition report that various polar groups are introduced film
2And NH
3The Cement Composite Treated by Plasma microporous polypropylene film, the result shows, the surface energy of microporous polypropylene film and corresponding wetting ability have significantly and improve, and compare with unmodified film, have higher flux recovery and low pollution index after cleaning.Yet the Cement Composite Treated by Plasma of different atmosphere is inevitable etching all, and the etching meeting causes to melt to be decreased and deposition; In addition, because the polar group adjustment member is regional or be hidden in microporous membrane inside, the lipophilicity of film can be recovered.In order to solve this two problems, people live with the plasma body circle at microporous polypropylene film surface physics absorption Polyvinylpyrolidone (PVP) (PVP) with the fixing method of plasmaassisted.The result shows, after the modification, the contact angle of film is along with the obvious reduction that increases of fixing percentage of grafting, and modified membrane has good biocompatibility and protein intercepts power, but the structure of PVP cross-linked layer is difficult to sign on film surface.Simultaneously, excessive radiation meeting causes the strength decreased of polymkeric substance.The body modification mostly is grafting, block modified method etc., Shi H etc. propose fusion-grafting methacrylic acid macrogol ester on the polyacrylic molecular chain at " Preparation of PP-g-PEG by using partial preirradiated polypropylene as initiator andits properties ", the graft copolymer of gained also can be used as the antipollution properties-correcting agent effect of polypropylene screen, but, the complicated mechanism of fusion-grafting, and be attended by serious side reaction, easily cause polyacrylic degraded.
In addition, because the synthetic of amphipathic nature polyalcohol generally all need to carry out in solvent, therefore need to be with a large amount of solvents as reaction medium, the application of solvent not only can be given environment, has also increased production cost.Tang smokes etc. and to have proposed to use the Solid-Phase Grafting of Methyl-Methacrylate vinyl pyrrolidone in " research of polypropylene grafted nitrogenous compound and antioxygen oil resistance thereof ", mentioned in the literary composition with nitrogen and come the protection system, but the flow velocity of nitrogen is difficult to control, and nitrogen is not easy fully to contact with polypropylene, thereby has influence on degradation-resistant effect; In addition, what this article adopted is that vacuum system is taken off benzene, and it is too quickly to heat, complicated operation inconvenience, and condition is harsh.Simultaneously, adopt stainless steel cauldron, system inside is heated inhomogeneous easily, and is difficult for fully mixing, and reaction has the dead angle.
Summary of the invention
Technical problem to be solved by this invention is: in the prior art, the synthetic of amphipathic nature polyalcohol generally all carries out in solvent, and the application of solvent has caused pollution to environment, has increased production cost; And in the prior art, with Solid-Phase Grafting of Methyl-Methacrylate hydrophile monomer, produce the method for amphipathic nature polyalcohol, and complicated operation, efficient is not high.
For solving this technical problem, and consider the theory of " Green Chemistry ", " green economy ", the technical solution used in the present invention is:
The invention provides a kind of polypropylene--hydrophilic monomer multipolymer, this multipolymer are the method preparations by solvent-free Banbury mixer solid phase synthesis.
The present invention also provides a kind of above-mentioned polypropylene--the preparation method of hydrophilic monomer multipolymer, and concrete steps are:
(1) take by weighing raw material according to following prescription, the mass fraction of each raw material is respectively,
100 parts of polypropylene
Interfacial agents 5-30 part
Initiator 0.1-9 part
Hydrophile monomer 10-60 part
Oxidation inhibitor 0.1-0.5 part,
As preferably: polypropylene is Powdered polypropylene, and particle diameter is 50-150 μ m,
Further: polypropylene is the F401 trade mark polypropylene that Yangzi Petrochemical Co., Ltd of China Petrochemical Industry produces,
As preferably: interfacial agents is selected from benzene, toluene or dimethylbenzene,
As preferably: initiator is selected from dibenzoyl peroxide BPO, tertiary butyl peroxidation formyl TBP, Diisopropyl azodicarboxylate AIBN or dicumyl peroxide DCP,
As preferably: the hydrophile monomer is selected from vinyl pyrrolidone NVP or hydroxyethyl methylacrylate HEMA,
As preferably: oxidation inhibitor is selected from antioxidant 1010 or antioxidant 1076;
(2) interfacial agents and polypropylene are mixed, carry out the swelling operation;
(3) polypropylene of the interfacial agents swelling being crossed, initiator, oxidation inhibitor and hydrophile monomer carry out graft polymerization reaction in Banbury mixer,
As preferably: the temperature of reaction of graft polymerization reaction is 100-120 ℃,
As preferably: the time that reaction is carried out is 1-3 hour;
(4) products therefrom is washed, purifies with dehydrated alcohol, filtration drying obtains polypropylene--the hydrophilic monomer amphipathic nature polyalcohol.
The invention has the beneficial effects as follows:
The present invention adopts the Banbury mixer solid phase grafting, without the synthetic polymkeric substance with amphipathic structure of solvent, does not have this problem of solvent contamination environment, is environmentally friendly synthesis technique.
Adopt the technique means of Banbury mixer graft polymerization, easy and simple to handle, reaction conditions there is not too much restriction; Come the protection system by adding oxidation inhibitor, there are two stirrers Banbury mixer inside, and mixing effect is good, and oxidation inhibitor can be contacted with material well, and system is heated evenly, and reacts more complete.
The present invention uses vinyl pyrrolidone NVP or hydroxyethyl methylacrylate HEMA as monomer, and monomer has carbon-carbon double bond, causes easily autohemagglutination, and grafted chain is lengthened, and increases hydrophilic radical, improves polyacrylic wetting ability.
Description of drawings
Fig. 1 is graft polymerization reaction equation of the present invention;
Fig. 2 is the polymer-modified infrared test figure that specific embodiment 1 prepares, and reacts after 3 hours, at 1660cm
-1The C=O characteristic peak appears.
Embodiment
Embodiment 1:
When the temperature of Banbury mixer reaches 100 ℃, 100 parts of (mass fractions, down together) the F401 trade mark polypropylene powder of Yangzi Petrochemical Co., Ltd of China Petrochemical Industry production is put into, splash into 10 parts interfacial agents dimethylbenzene with dropper, blend 2 hours, add 1 part BPO, 0.5 part of antioxidant 1010, splash at last 10 parts HEMA, reaction 3h.After reaction is finished, with absolute ethanol washing to removing monomer and homopolymer, last filtering drying.The quality m of weighing product.
Adopt iodimetry to survey percentage of grafting and grafting efficiency, take by weighing sample m
1(being no more than 10g), add water 100ml, the sodium-acetate 1g that adds some points promotes complexing action, then add iodine titration solution 10ml, concentration 0.1mol/l (c) places 10-20min, uses the Sulfothiorine titration, concentration 0.1mol/l, when red-brown disappears soon, add Starch Indicator 2ml, be titrated to again blue the disappearance.V: hypo solution uses volume, ml.Percentage of grafting calculates by following formula:
The percentage of grafting of products therefrom sees the following form 1.
Polypropylene after the modification is placed on 85 ℃ of temperature, humidity 85%, and 1000h measures the percentage of grafting after processing, and investigates the stability of product.The results are shown in Table 1.
Embodiment 2:
When the temperature of Banbury mixer reaches 100 ℃, the F401 trade mark polypropylene powder that 100 parts of Yangzi Petrochemical Co., Ltd of China Petrochemical Industry produce is put into, splash into 30 parts interfacial agents dimethylbenzene with dropper, blend 10 minutes, make the abundant swelling of polypropylene, add 1 part BPO, 0.5 part of antioxidant 1010, splash at last 10 parts NVP, reaction 2h.After reaction was finished, it was dry to purify, the percentage of grafting testing method of products therefrom as described in Example 1, test result sees the following form 1.
Polypropylene after the modification is placed on 85 ℃ of temperature, humidity 85%, and 1000h measures the percentage of grafting after processing, and investigates the stability of product.The results are shown in Table 1.
Embodiment 3:
When the temperature of Banbury mixer reaches 110 ℃, the F401 trade mark polypropylene powder that 100 parts of Yangzi Petrochemical Co., Ltd of China Petrochemical Industry produce is put into, splash into 5 parts interfacial agents dimethylbenzene with dropper, blend 10 minutes, make the abundant swelling of polypropylene, add 0.1 part DCP, 0.5 part of antioxidant 1010, splash at last 20 parts NVP, reaction 1h.After reaction was finished, it was dry to purify, the percentage of grafting testing method of products therefrom as described in Example 1, test result sees the following form 1.
Polypropylene after the modification is placed on 85 ℃ of temperature, humidity 85%, and 1000h measures the percentage of grafting after processing, and investigates the stability of product.The results are shown in Table 1.
Embodiment 4:
When the temperature of Banbury mixer reaches 100 ℃, the F401 trade mark polypropylene powder that 100 parts of Yangzi Petrochemical Co., Ltd of China Petrochemical Industry produce is put into, splash into 10 parts interfacial agents toluene with dropper, blend 10 minutes, make the abundant swelling of polypropylene, add 6 parts AIBN, 0.5 part of antioxidant 1010, splash at last 10 parts NVP, reaction 2h.After reaction was finished, it was dry to purify, the percentage of grafting testing method of products therefrom as described in Example 1, test result sees the following form 1.
Polypropylene after the modification is placed on 85 ℃ of temperature, humidity 85%, and 1000h measures the percentage of grafting after processing, and investigates the stability of product.The results are shown in Table 1.
Embodiment 5:
When the temperature of Banbury mixer reaches 100 ℃, the F401 trade mark polypropylene powder that 100 parts of Yangzi Petrochemical Co., Ltd of China Petrochemical Industry produce is put into, splash into 20 parts interfacial agents dimethylbenzene with dropper, blend 10 minutes, make the abundant swelling of polypropylene, add 1 part BPO, 0.1 part of antioxidant 1010, after splash into 10 parts NVP, the reaction 2h.After reaction was finished, it was dry to purify, the percentage of grafting testing method of products therefrom as described in Example 1, test result sees the following form 1.
Polypropylene after the modification is placed on 85 ℃ of temperature, humidity 85%, and 1000h measures the percentage of grafting after processing, and investigates the stability of product.The results are shown in Table 1.
Embodiment 6:
When the temperature of Banbury mixer reaches 100 ℃, the F401 trade mark polypropylene powder that 100 parts of Yangzi Petrochemical Co., Ltd of China Petrochemical Industry produce is put into, splash into 10 parts interfacial agents dimethylbenzene with dropper, blend 10 minutes, make the abundant swelling of polypropylene, add 9 parts TBP, 0.1 part of antioxidant 1076, splash at last 60 parts NVP, reaction 2h.After reaction was finished, it was dry to purify, the percentage of grafting testing method of products therefrom as described in Example 1, test result sees the following form 1.
Polypropylene after the modification is placed on 85 ℃ of temperature, humidity 85%, and 1000h measures the percentage of grafting after processing, and investigates the stability of product.The results are shown in Table 1.
Embodiment 7:
When the temperature of Banbury mixer reaches 120 ℃, the F401 trade mark polypropylene powder that 100 parts of Yangzi Petrochemical Co., Ltd of China Petrochemical Industry produce is put into, splash into 10 parts interfacial agents benzene with dropper, blend 10 minutes, make the abundant swelling of polypropylene, add 1 part BPO, 0.1 part of antioxidant 1010, splash at last 20 parts HEMA, reaction 1h.After reaction was finished, it was dry to purify, the percentage of grafting testing method of products therefrom as described in Example 1, test result sees the following form 1.
Polypropylene after the modification is placed on 85 ℃ of temperature, humidity 85%, and 1000h measures the percentage of grafting after processing, and investigates the stability of product.The results are shown in Table 1.
Table 1
Claims (10)
1. polypropylene--the hydrophilic monomer multipolymer is characterized in that: described polypropylene--hydrophilic monomer multipolymer is the method preparation by the Banbury mixer solid phase synthesis.
2. polypropylene as claimed in claim 1--the preparation method of hydrophilic monomer multipolymer is characterized in that: described preparation method is,
(1) take by weighing raw material according to following prescription, the mass fraction of each raw material is respectively,
100 parts of polypropylene
Interfacial agents 5-30 part
Initiator 0.1-9 part
Hydrophile monomer 10-60 part
Oxidation inhibitor 0.1-0.5 part;
(2) interfacial agents and polypropylene are mixed, carry out the swelling operation;
(3) polypropylene of the interfacial agents swelling being crossed, initiator, oxidation inhibitor and hydrophile monomer carry out graft polymerization reaction in Banbury mixer;
(4) products therefrom is washed, purifies with dehydrated alcohol, filtration drying obtains polypropylene--the hydrophilic monomer amphipathic nature polyalcohol.
3. polypropylene as claimed in claim 2--the preparation method of hydrophilic monomer multipolymer is characterized in that: described polypropylene is Powdered polypropylene, and particle diameter is 50-150 μ m.
4. polypropylene as claimed in claim 3--the preparation method of hydrophilic monomer multipolymer is characterized in that: described polypropylene is the F401 trade mark polypropylene that Yangzi Petrochemical Co., Ltd of China Petrochemical Industry produces.
5. polypropylene as claimed in claim 2--the preparation method of hydrophilic monomer multipolymer is characterized in that: described interfacial agents is selected from benzene, toluene or dimethylbenzene.
6. polypropylene as claimed in claim 2--the preparation method of hydrophilic monomer multipolymer is characterized in that: described initiator is selected from dibenzoyl peroxide BPO, tertiary butyl peroxidation formyl TBP, Diisopropyl azodicarboxylate AIBN or dicumyl peroxide DCP.
7. polypropylene as claimed in claim 2--the preparation method of hydrophilic monomer multipolymer is characterized in that: described hydrophile monomer is selected from vinyl pyrrolidone NVP or hydroxyethyl methylacrylate HEMA.
8. polypropylene as claimed in claim 2--the preparation method of hydrophilic monomer multipolymer is characterized in that: described oxidation inhibitor is selected from antioxidant 1010 or antioxidant 1076.
9. polypropylene as claimed in claim 2--the preparation method of hydrophilic monomer multipolymer is characterized in that: the temperature of reaction of the graft polymerization reaction described in the step (3) is 100-120 ℃.
10. polypropylene as claimed in claim 2--the preparation method of hydrophilic monomer multipolymer is characterized in that: the time that the reaction described in the step (3) is carried out is 1-3 hour.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558426A (en) * | 2015-01-06 | 2015-04-29 | 东北石油大学 | Preparation method of polar polypropylene |
| CN106279544A (en) * | 2016-08-19 | 2017-01-04 | 中国科学院化学研究所 | The ultra-fine polyolefin of graft modification and solid phase grafting method thereof |
| CN107974831A (en) * | 2016-10-24 | 2018-05-01 | 中国石油化工股份有限公司 | Polypropylene non-woven fabric that a kind of calcium alginate is modified and preparation method thereof |
| CN113563530A (en) * | 2020-04-29 | 2021-10-29 | 中国石油化工股份有限公司 | Modified material of polypropylene grafted heterocycle, preparation method and application thereof |
| CN113897018A (en) * | 2021-08-27 | 2022-01-07 | 湖北晟徕复合材料有限公司 | Hydrophilic and antibacterial modified polypropylene material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831132A (en) * | 2010-05-21 | 2010-09-15 | 中国科学院长春应用化学研究所 | Resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101831132A (en) * | 2010-05-21 | 2010-09-15 | 中国科学院长春应用化学研究所 | Resin composition |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558426A (en) * | 2015-01-06 | 2015-04-29 | 东北石油大学 | Preparation method of polar polypropylene |
| CN106279544A (en) * | 2016-08-19 | 2017-01-04 | 中国科学院化学研究所 | The ultra-fine polyolefin of graft modification and solid phase grafting method thereof |
| CN106279544B (en) * | 2016-08-19 | 2019-03-12 | 中国科学院化学研究所 | The ultra-fine polyolefin of graft modification and its solid phase grafting method |
| CN107974831A (en) * | 2016-10-24 | 2018-05-01 | 中国石油化工股份有限公司 | Polypropylene non-woven fabric that a kind of calcium alginate is modified and preparation method thereof |
| CN107974831B (en) * | 2016-10-24 | 2020-12-18 | 中国石油化工股份有限公司 | Calcium alginate modified polypropylene fiber non-woven fabric and preparation method thereof |
| CN113563530A (en) * | 2020-04-29 | 2021-10-29 | 中国石油化工股份有限公司 | Modified material of polypropylene grafted heterocycle, preparation method and application thereof |
| CN113897018A (en) * | 2021-08-27 | 2022-01-07 | 湖北晟徕复合材料有限公司 | Hydrophilic and antibacterial modified polypropylene material and preparation method thereof |
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