CN109608581A - A kind of synthetic method of chlorination maleic anhydride inoculated polypropylene - Google Patents
A kind of synthetic method of chlorination maleic anhydride inoculated polypropylene Download PDFInfo
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- CN109608581A CN109608581A CN201811430441.XA CN201811430441A CN109608581A CN 109608581 A CN109608581 A CN 109608581A CN 201811430441 A CN201811430441 A CN 201811430441A CN 109608581 A CN109608581 A CN 109608581A
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- maleic anhydride
- polypropylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
- C08F8/22—Halogenation by reaction with free halogens
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention provides a kind of synthetic methods of chlorination maleic anhydride inoculated polypropylene.Method includes the following steps: a certain proportion of polypropylene, maleic anhydride and chlorinated solvents are put into three-necked flask by (1), it is stirred, 120-130 DEG C of reaction temperature of control, after polypropylene is completely dissolved, the chlorinated solvents solution for containing a certain amount of initiator is instilled, polypropylene grafted maleic anhydride is carried out and reacts 2-4h;(2) the chlorinated solvents solution containing a certain amount of initiator is instilled again, it is passed through chlorine and carries out chlorination reaction 2-4h, a period of time 0.5-2h that stops after logical chlorine that the reaction was continued, stop heating, remaining chlorine is driven away with nitrogen, precipitated product, to eliminate impurity, is dried in vacuo the chlorination maleic anhydride inoculated polypropylene to get purifying by multiple washing of precipitate by chlorizate.The method of the present invention is simple, at low cost, and product maleic anhydride grafting ratio is higher, can be widely applied to the fields such as adhesive, coating, ink and solubilizer.
Description
Technical field
The invention belongs to chemical fields, and in particular to a kind of synthesis side of chlorination maleic anhydride inoculated polypropylene
Method.
Background technique
Polypropylene (PP) is one of the thermoplastic macromolecule material of current most development prospect, because its density is small, is easy to add
Work molding, the advantages that product is non-toxic and tasteless, cheap and be widely used in the industries such as automobile, electronics and toy.With people
The raising of aesthetic consciousness, it is also higher and higher to the surface property and appearance requirement of plastic products, in order to improve the market competition of PP
Power needs to carry out top finishing to PP.PP is non-polar plastic, and crystallinity is high, surface tension is low, it is wetted to be difficult to, and coating exists
Adhere on PP ground difficult, it usually needs using chlorinated polypropylene (CPP) to improve adhesive force of the coating on PP ground, still
There is also some unsatisfactory places in use by CPP, comprising: 1) small to the adhesive force of polar material;2) and it is many
Resin compatible is not good enough;3) solubility is low in polar solvent;4) it is used as priming paint, it is ply adhesion with other coatings, resistance to
Oiliness, water resistance are insufficient;These are mainly caused by CPP molecular polarity is small.In order to improve CPP and other resins compatibility,
Improve CPP and other coatings adhesive force, can by CPP molecule grafted polar group, increase CPP molecular polarity come reality
It is existing.In the monomer of numerous polar functionalities, the most commonly used is the monomers for having acid anhydrides, carboxyl or acrylic acid groups, wherein polarity
Maleic anhydride (MAH) that is big and being not easy autohemagglutination is more common.
Currently, chlorination maleic anhydride inoculated polypropylene be mostly using modified polypropylene (i.e. maleic anhydride inoculated polypropylene,
Melt grafting) directly pass through solwution method or gas-solid method as raw material and carries out what chlorination reaction obtained, this method exists former
The problems such as range of choice of material maleic anhydride inoculated polypropylene is narrow, grafting rate is low is not able to satisfy more production needs.
Therefore, it is badly in need of a kind of efficient, the alternative wide chlorination maleic anhydride inoculated polypropylene of raw material synthesis side
Method.
Summary of the invention
The present invention provides a kind of synthetic methods of chlorination maleic anhydride inoculated polypropylene, and this method is simple, at low cost, obtain
Maleic anhydride grafting ratio it is higher, be that a kind of economical and efficient, the alternative wide chlorination maleic anhydride grafting of raw material are poly-
The synthetic method of propylene.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of synthetic method of chlorination maleic anhydride inoculated polypropylene, includes the following steps:
(1) a certain proportion of polypropylene, maleic anhydride and chlorinated solvents are put into reaction vessel, are stirred, controlled
120-130 DEG C of reaction temperature, after polypropylene is completely dissolved, the chlorinated solvents solution for containing a certain amount of initiator is instilled, is carried out
Polypropylene grafted maleic anhydride reacts 2-3h;
(2) continue to instill the chlorinated solvents solution for containing a certain amount of initiator into reaction vessel, be passed through chlorine and carry out chlorine
Change reaction 2-3h, a period of time 0.5-2h that stops after logical chlorine that the reaction was continued stops heating, drives remaining chlorine away with nitrogen;
(3) chlorizate obtained carries out washing of precipitate by acetone and dehydrated alcohol mixed liquor, then again with enough
Chlorinated solvents are heated to precipitated product and are completely dissolved, and carry out washing of precipitate, repeat number using acetone and dehydrated alcohol mixed liquor
It is secondary, to eliminate impurity, precipitated product is dried in vacuo the chlorination maleic anhydride inoculated polypropylene to get purifying.
Further, the polypropylene being added in the step (1) is isotactic polypropylene.
Further, the polypropylene that is added in the step (1), maleic anhydride, chlorinated solvents quality, in parts by weight
Meter is respectively as follows: 100 parts by weight of polypropylene, and maleic anhydride 5-20 parts by weight, 1950 parts by weight of chlorinated solvents, step (1), (2) add
The chlorinated solvents solution containing initiator entered each means 25 parts by weight of chlorinated solvents containing 0.5 parts by weight initiator.
Further, the step (1), (2), the chlorinated solvents being added in (3) or contain chlorine containing a certain amount of initiator
Any one of chlorinated solvents in 1,1,2- trichloroethanes, 1,1,2,2- tetrachloroethanes in solvent, and each step makes
Chlorinated solvents type may be the same or different.
Further, it is cumyl peroxide or dibenzoyl peroxide that initiator is added in the step (1).
Further, the step (2) is passed through the time of chlorine as 2-3h.
Further, the acetone in the step (3) and dehydrated alcohol mixed liquor are by acetone and dehydrated alcohol by volume
Than being obtained for 1: 1 mixed preparing.
Compared with prior art, beneficial effects of the present invention:
(1) present invention uses 1,1,2- trichloroethanes or 1, and 1,2,2- tetrachloroethanes can substitute completely as reaction dissolvent
Carbon tetrachloride, and carbon tetrachloride will not be generated during the preparation process, environmentally protective, the use of solvent is not by environmental protection pact
Limitation, has a vast market application prospect and more profound significance;
(2) preparation method provided by the invention successively carries out graft reaction and chlorination reaction in a reaction vessel,
The cost of raw material and time cost, economical and efficient are saved;
(3) preparation method provided by the invention can choose different raw material polypropylene, by the difference for selecting substrate
The product of available diversification performance meets the adhesive property requirement of different industries.
(4) add initiator by several times in preparation method provided by the invention, ensure that two secondary responses initiator activity and
Efficiency, makes that properties of product are more preferable and quality is stablized;
Specific embodiment
The present invention is further elaborated combined with specific embodiments below.
One, embodiment is prepared
Embodiment 1
It is added in the three-necked flask of 500mL, is to slowly warm up to firstly, weighing 20g PP, 1g MAH and 400g tetrachloroethanes
120 DEG C, 1h is stirred after polypropylene is completely dissolved, and is being condensed back and at the uniform velocity under stirring condition, 5g is being added dropwise and contains 0.1g peroxide
Change the tetrachloroethanes solution of diisopropylbenzene (DIPB), control temperature reacts 2h in 120 DEG C of progress polypropylene grafted maleic anhydrides;Wait react knot
Shu Hou, then the tetrachloroethanes solution that 5g contains 0.1g cumyl peroxide is added dropwise, chlorine 2h progress is continually fed at 120 DEG C
Chlorination reaction is kept stirring 0.5h after stopping logical chlorine at such a temperature, stops heating, be passed through dry nitrogen 30min to catch up with
Remaining chlorine is walked, after reaction, product passes through acetone and dehydrated alcohol mixed liquor washing of precipitate, then molten with tetrachloroethanes heating
Solution, using acetone and dehydrated alcohol mixed liquor washing of precipitate after dissolution, is repeated several times, to eliminate impurity, by precipitated product room
The rice white chlorination maleic anhydride inoculated polypropylene to get purifying is dried in vacuo under temperature.
The MAH grafting rate of products therefrom is 6.1%, chlorinity 26.32%.
Embodiment 2
It is added in the three-necked flask of 500mL, is to slowly warm up to firstly, weighing 20g PP, 2g MAH and 400g tetrachloroethanes
122 DEG C, 1h is stirred after polypropylene is completely dissolved, and is being condensed back and at the uniform velocity under stirring condition, 5g is being added dropwise and contains 0.1g peroxide
Change the tetrachloroethanes solution of diisopropylbenzene (DIPB), control temperature reacts 3h in 120 DEG C of progress polypropylene grafted maleic anhydrides;Wait react knot
Shu Hou, then the tetrachloroethanes solution that 5g contains 0.1g cumyl peroxide is added dropwise, chlorine 3h progress is continually fed at 122 DEG C
Chlorination reaction is kept stirring 1h after stopping logical chlorine at such a temperature, stops heating, be passed through dry nitrogen 30min to drive away
Remaining chlorine, after reaction, product pass through acetone and dehydrated alcohol mixed liquor washing of precipitate, then molten with tetrachloroethanes heating
Solution, using acetone and dehydrated alcohol mixed liquor washing of precipitate after dissolution, is repeated several times, to eliminate impurity, by precipitated product room
The rice white chlorination maleic anhydride inoculated polypropylene to get purifying is dried in vacuo under temperature, the MAH grafting rate of product is
8.3%, chlorinity 26.01%.
Embodiment 3
It is added in the three-necked flask of 500mL, is to slowly warm up to firstly, weighing 20g PP, 4g MAH and 400g tetrachloroethanes
126 DEG C, 1h is stirred after polypropylene is completely dissolved, and is being condensed back and at the uniform velocity under stirring condition, 5g is being added dropwise and contains 0.1g peroxide
Change the tetrachloroethanes solution of diisopropylbenzene (DIPB), control temperature reacts 2h in 126 DEG C of progress polypropylene grafted maleic anhydrides;Wait react knot
Shu Hou, then the tetrachloroethanes solution that 5g contains 0.1g cumyl peroxide is added dropwise, chlorine 3h progress is continually fed at 126 DEG C
Chlorination reaction is kept stirring 2h after stopping logical chlorine at such a temperature, stops heating, be passed through dry nitrogen 30min to drive away
Remaining chlorine, after reaction, product pass through acetone and dehydrated alcohol mixed liquor washing of precipitate, then molten with tetrachloroethanes heating
Solution, using acetone and dehydrated alcohol mixed liquor washing of precipitate after dissolution, is repeated several times, to eliminate impurity, by precipitated product room
The rice white chlorination maleic anhydride inoculated polypropylene to get purifying is dried in vacuo under temperature;.
The MAH grafting rate of products therefrom is 8.94%, chlorinity 28.15%.
Although having done more detailed elaboration to technical solution of the present invention and having enumerated, it should be understood that for ability
For field technique personnel, modifications to the embodiments described above may be made or uses equivalent alternative solution, this is to those skilled in the art
It is it is clear that these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to the present invention for member
Claimed range.
Claims (8)
1. a kind of synthetic method of chlorination maleic anhydride inoculated polypropylene, which comprises the following steps:
(1) polypropylene, maleic anhydride and chlorinated solvents are placed in same reaction vessel, heated and are stirred, to polypropylene
After being completely dissolved, the chlorinated solvents for containing a certain amount of initiator are instilled, polypropylene grafted maleic anhydride is carried out and reacts 2-3h;
(2) continue to instill the chlorinated solvents for containing a certain amount of initiator into the container of step (1), it is anti-to be passed through chlorine progress chlorination
Answer 2-3h, a period of time 0.5-2h that stops after logical chlorine that the reaction was continued stops heating, drives remaining chlorine away.
2. a kind of synthetic method of chlorination maleic anhydride inoculated polypropylene according to claim 1, which is characterized in that described
The polypropylene being added in step (1) is isotactic polypropylene.
3. a kind of synthetic method of chlorination maleic anhydride inoculated polypropylene according to claim 1, which is characterized in that described
Polypropylene, the maleic anhydride, chlorinated solvents being added in step (1) are respectively as follows: 100 parts by weight of polypropylene according to parts by weight,
Maleic anhydride 5-20 parts by weight, 1950 parts by weight of chlorinated solvents, the chlorinated solvents solution containing initiator that step (1), (2) are added
Each mean 25 parts by weight of chlorinated solvents containing 0.5 parts by weight initiator.
4. a kind of synthetic method of chlorination maleic anhydride inoculated polypropylene according to claim 1, which is characterized in that described
Chlorinated solvents in step (1), (2) in chlorinated solvents or chlorinated solvents containing a certain amount of initiator are selected from 1,1,2- tri- chloroethene
Alkane, 1,1,2,2- tetrachloroethanes any one, and the chlorinated solvents that each step uses may be the same or different.
5. a kind of synthetic method of chlorination maleic anhydride inoculated polypropylene according to claim 1, which is characterized in that described
Initiator in step (1), (2) is cumyl peroxide or dibenzoyl peroxide, and the initiator that each step uses can
It is identical or different.
6. a kind of synthetic method of chlorination maleic anhydride inoculated polypropylene according to claim 1, which is characterized in that described
The time that chlorine is passed through in step (2) is 2-3h.
7. a kind of synthetic method of chlorination maleic anhydride inoculated polypropylene according to claim 1, which is characterized in that described
The purification step for the chlorizate that step (2) obtains is as follows:
The chlorizate that step (2) obtains carries out washing of precipitate by acetone and dehydrated alcohol mixed liquor, then again with molten containing chlorine
Agent dissolves by heating precipitated product, carries out washing of precipitate using acetone and dehydrated alcohol mixed liquor, is repeated several times, miscellaneous to eliminate
Precipitated product is dried in vacuo the chlorination maleic anhydride inoculated polypropylene to get purifying by matter.
8. a kind of synthetic method of chlorination maleic anhydride inoculated polypropylene according to claim 7, which is characterized in that described
It is that 1:1 mixed preparing obtains that acetone and dehydrated alcohol mixed liquor are by acetone and dehydrated alcohol by volume.
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101555301A (en) * | 2009-05-19 | 2009-10-14 | 中山大学 | Method for preparing solid phase of chlorinated polypropylene or chlorinated maleic anhydride inoculated polypropylene |
CN104356304A (en) * | 2014-10-26 | 2015-02-18 | 大足县众科管道设备有限公司 | Synthesis method of maleic anhydride grafted chlorinated polypropylene used for plastic coating |
-
2018
- 2018-11-27 CN CN201811430441.XA patent/CN109608581A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101555301A (en) * | 2009-05-19 | 2009-10-14 | 中山大学 | Method for preparing solid phase of chlorinated polypropylene or chlorinated maleic anhydride inoculated polypropylene |
CN104356304A (en) * | 2014-10-26 | 2015-02-18 | 大足县众科管道设备有限公司 | Synthesis method of maleic anhydride grafted chlorinated polypropylene used for plastic coating |
Non-Patent Citations (2)
Title |
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聂建华,等: "塑料涂料用马来酸酐接枝氯化聚丙烯的合成与性能", 《电镀与涂饰》 * |
谭晓明,等: "聚丙烯溶液法接枝马来酸酐及其表征", 《培训与研究湖北教育学院学报》 * |
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