WO2012139327A1 - Free-radical polymerizaiton initiator composition and uses thereof - Google Patents

Abstract

A free-radical polymerization initiator composition consisting of a low temperature initiator with decomposition temperature lower than 60℃ and a high temperature initiator with decomposition temperature higher than 70℃ is disclosed. The use of the free-radical initiator composition for preparing copolymer of vinyl ether (ester) and maleic anhydride is also disclosed, wherein the content of the free-radical initiator composition is 0.1-10.0‰ of the total mass of the reaction system. The initiator composition of the invention can extend the polymerization time at low temperature, reduce the polymerization time at high temperature, and improve the stability of the polymerization reaction. The total polymerization time is relatively shortened and the energy consumption is low. The polymer obtained has excellent quality and high viscosity, and is environmentally friendly.

Description

 Instruction manual

 White-based polymerization initiator composition and fine technical field thereof

 The invention belongs to the field of chemical industry, relates to a radical polymerization initiator composition and application thereof, and particularly relates to a radical polymerization initiator composition and a preparation thereof for preparing a polymer compound olefin ether-butenedic anhydride copolymer Application in . Prepare

 Prepare

Background technique

The butyric acid anhydride has strong adhesion and excellent scale inhibition performance. The polymer compound obtained by copolymerizing butylene dianhydride with an olefinic substance has a unique scale inhibition effect and can inhibit the scale of certain zinc salts and calcium salts. Deposition. Such a copolymer combines the advantages of polybutylene anhydride and polymerized olefins, fg^ excellent adhesive materials and scale inhibitors, and is widely used for the modification of polymer compounds, and has a broad market prospect. For example: grafting butane dianhydride to the anhydride of the macromolecule of polypropylene to increase the polarity of the molecular chain, effectively improve its compatibility with polar materials, thereby improving its hydrophilicity, dyeability, antistatic Sex, adhesive, printability ft wide range of polypropylene applications or improve its performance. Prepare

 Polybutylene anhydride

 Olefin butadiene anhydride copolymer preparation

«The butene phthalic anhydride copolymer is an amphoteric polymer. The isobutylene segment has strong lipophilicity in the structure. The butadiene anhydride segment has good hydrophilicity, so it can be used after ammonium salting. Disperse red lake pigments, which can be used as superabsorbent resin, as a viscosity reducer for drilling fluids, cement pastes, and water treatment agents. Its properties are strongly related to the copolymerization ratio of isobutylene and butenedic anhydride, the distribution of two monomers in the polymer chain, and the molecular weight. It maintains the good elasticity of polyisobutylene and has good heat resistance, light resistance and oxidation resistance. In view of the fact that it can increase the hardness and viscosity of polyvinyl acetate adhesive, increase the viscosity of acrylic emulsion, emulsion type adhesive of styrene-butadiene rubber, dispersant of inorganic functional filler, formaldehyde-free adhesive, water resistance at the same time as polyvinyl alcohol Excellent emulsification and dispersibility, and can form a good film on the metal surface. Wide range Protective adhesive for polymeric latex, emulsion adhesive for wood and paper, water based adhesive for ceramic powder, coating for thermal paper, microcapsule coating for pressure sensitive paper, forging lubricant, steel Hardener, etc. Road

^^^ Ethylene phthalic anhydride copolymer is applied to road marking materials, filled composite materials of styrene, wood, etc. The products of the ethylene-butenedonic anhydride copolymer are generally hard, have a low viscosity, and have a low melting point. Products can be used in adhesives, coatings, wrapping paper, color concentrates and plastics processing. Road

 Ethylene butyrene anhydride copolymer

 Vinyl Acetate The butadiene anhydride copolymer is a very powerful mud thinner. Solve the problem of scaling on the surface of the formation, wellbore and ground pipelines during oilfield development. Fouling not only causes equipment corrosion, oil production volume drops 3⁄4 and seriously affects the normal operation of oil field production. Controlling fouling has become one of the important problems in oilfield development. Butenic acid anhydride-vinyl acetate copolymer is widely used in water treatment of oilfields. Road

 Vinyl acetate butadiene anhydride copolymer channel

 Due to the shortcomings of polystyrene brittleness, low strength, and poor heat resistance, the application is limited. The new thermoplastic engineering plastic styrene-butenedic anhydride random copolymer «copolymerized by the copolymerization of butenedic anhydride" has improved heat resistance. Good heat resistance Low melt viscosity «Different processing properties ^ Blend with a variety of polymer materials. At the same time, its foaming properties, chemical stability, transparency and hardness are also good. It is mainly used in automobile manufacturing, household appliances, building materials and office supplies. It is also widely used in water treatment agents, emulsifiers for pesticides, and curing agents for epoxy resins. Road

 Styrene butadiene anhydride copolymer channel

Alkyl vinyl ether butadiene anhydride copolymer: methyl vinyl ether butadiene anhydride copolymer, ethyl vinyl ether Adipic anhydride copolymer, n-propyl vinyl ether butenedeic anhydride copolymer, isopropyl vinyl ether butenedic anhydride copolymer, n-butyl vinyl ether butened phthalic anhydride copolymer, isobutyl vinyl Ether butadiene anhydride copolymers, etc., because of their good chemical stability, adhesion, cohesiveness, water retention and film formation, and non-toxic and harmless to human body, have been used in medicine, agriculture and fine chemicals. Many fields have been widely used. Fight

 ( : «, * , "««, «««, for drilling, occupying, etc.)

 Alkyl vinyl ether IT enedic anhydride copolymer expansion

The mercapto vinyl methyl ether butadiene anhydride copolymer is a water-soluble electrolyte and its physical and chemical properties are similar to those of another water-soluble polymer series. It is one of the few synthetic compounds that are non-toxic and harmless to humans and animals. . Due to its good chemical stability, low toxicity, biocompatibility, complexation, chelating, adhesive, cohesive, film-forming properties (the film is easily peeled off), both hydrophilic and hydrophobic Unique properties, this product has a wide range of applications in modern industry, can play the role of dispersants, coupling agents, stabilizers, thickeners, emulsifiers, solubilizers, corrosion inhibitors, film formers and antistatic agents . It can be used in oral care, as well as in adhesives and coatings, chemical processes such as pesticides, herbicides, sprays, soil conditioners, polymerization, latex, water treatment, compound detergents, hand sanitizers, makeup and toiletries, Foam fire extinguishing agents, leather tanning and paper industry, pharmaceuticals, etc., can also be used in the processing of waxes and polishes, ceramics, asbestos and steel. Expand

Before the tears, about the synthesis of olefin butadiene hydride copolymers, a large number of literatures provide solvent methods, such as toluene, benzene, ethyl acetate, methyl formate, amyl butyrate, propyl acetate, cyclohexane Acetone, methyl tert-butyl ether, methyl ethyl ketone, ethyl acetate and heptane are used as polymerization media, and common peroxides: benzoyl peroxide, azobisisoheptanenitrile, tert-butyl peroxypivalate An ester, a dodecyl peroxide or the like is used as an initiator, and an alkyl vinyl ether and a butened dianhydride are obtained by polymerization. Expand

The US patents, m, mm, nm^, m, m, mms, and sorption are all provided by the polymerization of aromatic solvents (benzene or toluene) as a medium, which inevitably produces solvent residues. Quality and safety pose serious risks, and the production process will also have an adverse impact on the environment. For example, the preparation of a copolymer of vinyl methyl ether butadiene anhydride is carried out by using benzene or toluene as a solvent, and a single initiator such as benzoyl peroxide, azobisisoheptanenitrile or dodecyl peroxide to carry out polymerization. Expand

 For example, the conventional preparation method of the butadiene anhydride-vinyl acetate copolymer is to initiate polymerization by using a single initiator, benzoic anhydride (BPO) or the like, and generally uses an organic solvent such as toluene or benzene as a medium.

 Free radical polymerization is the earliest and most widely used polymerization reaction in industrialization. A free radical initiator refers to a kind of compound which is easily decomposed into a free radical by heat, and is commonly used for initiating radical polymerization and copolymerization of an ethylenic or diene monomer, and also for crosslinking curing and polymer of an unsaturated polyester. Cross-linking reaction. Free radical initiators are classified according to their temperature range: 1) high temperature initiators, such as alkyl peroxides, alkyl hydroperoxides, peroxyesters, etc.; 2) low temperature initiators, such as bicarbonate dihydrate Ethyl ester (DCPD), bis(2-ethylhexyl) peroxydicarbonate (B"P). Table 1 shows the initiation temperatures for the different half-lives of commonly used initiators.

 Table 1. Initiator temperature

 Decomposition temperature rc)

T _1/2 =1 h T _1/2 =5h T _1/2 =10h

 TBCP 59 48 43

 DCPD 60 49 44

 I PP 61 50 45

 A / N 64 53~55 47

 B-P 64 - 47

 BPP 73 60 55

 LPO 79 67 61

 AB N 82 70 64

 BPO 92 80 72

 BPB 124 110 105

CBPB 122 112 110 134 122 106

 DCP 135 122 1 15

 DTBP 148 132 127

 The initiator is usually selected according to the temperature requirements of the polymerization reaction. If the high temperature initiator is used in the low temperature range, the decomposition rate is too low, and the polymerization time is prolonged; if the low temperature initiator is used in the high temperature range polymerization, the decomposition rate is too fast, the initiator is consumed prematurely, and in the low polymerization conversion stage Stop the reaction.

 Compared with a single initiator, the composite initiator is rarely studied. The effect on process, engineering, cost and product quality is also unmatched by a single initiator. The complex initiator will become an important development direction of the polymerization reaction. . Summary of the invention

 SUMMARY OF THE INVENTION An object of the present invention is to provide a radical polymerization initiator composition in view of the above disadvantages of the prior art.

 Another object of the present invention is to provide an application of the radical polymerization initiator composition.

 It is still another object of the present invention to provide a process for producing an alkenyl (e.g.)-butenedic acid anhydride copolymer using the radical polymerization initiator composition.

 The object of the present invention can be achieved by the following technical solutions:

 A radical polymerization initiator composition, which is prepared by compounding a low temperature initiator with a high temperature initiator, wherein the low temperature initiator refers to an initiator having a decomposition temperature lower than 60 ° C, The high temperature initiator refers to an initiator having a decomposition temperature higher than 70 °C.

 The low temperature initiator is selected from the group consisting of dicycloethyl peroxydicarbonate (DCPD), azobisisoheptanenitrile (A / N), bis(2-ethylhexyl) peroxydicarbonate (B"P) And di(t-butylcyclohexyl peroxydicarbonate) (TBCP), diisopropyl peroxydicarbonate (I PP), the high temperature initiator is selected from the group consisting of: dodecyl peroxide (LPO), azodi Isobutyronitrile (AB N), dibenzoyl peroxide (BP〇), tert-butyl peroxybenzoate (BPB), 2,2-di(tert-butylperoxy)butane (CBPB), peroxidation Methyl ethyl ketone (^B<P).

The radical polymerization initiator composition is selected from the group consisting of a combination of dodecyl peroxide and di(p-butylcyclohexyl peroxydicarbonate), a dodecyl peroxide and a bicarbonate A composition obtained by compounding hexyl ester, a combination of dodecyl peroxide and diisopropyl peroxydicarbonate, a combination of dodecanoyl peroxide and azobisisoheptonitrile a composition of a combination of dodecyl peroxide and bis(2-ethylhexyl) peroxydicarbonate, azobisisobutyronitrile and di(p-butylcyclohexyl)peroxydicarbonate a composition obtained by combining a composition of azobisisobutyronitrile with dicyclohexyl peroxydicarbonate, a combination of azobisisobutyronitrile and diisopropyl peroxydicarbonate , azobisisobutyronitrile and azobis A composition obtained by compounding heptonitrile, azobisisobutyronitrile and bis(peroxydicarbonate), strong ethylhexyl 11 composition, dibenzoyl peroxide and diperoxydicarbonate A composition obtained by compounding p-tert-butylcyclohexyl ester, a combination of dibenzoyl peroxide and dicyclohexyl peroxydicarbonate, dibenzoyl peroxide and diisopropyl peroxydicarbonate A composition obtained by compounding an ester, a composition obtained by compounding dibenzoyl peroxide and azobisisoheptanenitrile, dibenzoyl peroxide and diperoxydicarbonate, and strong ethylhexyl 11 a composition obtained by compounding tert-butyl peroxybenzoate with p-tert-butylcyclohexyl peroxydicarbonate, tert-butyl peroxybenzoate and dicyclohexyl peroxydicarbonate a compounded composition, a combination of tert-butyl peroxybenzoate and diisopropyl peroxydicarbonate, a mixture of tert-butyl peroxybenzoate and azobisisoheptonitrile Composition of the composition, tert-butyl peroxybenzoate and bis(peroxydicarbonate) strong ethylhexyl 11 Digging 2) a combination of tert-butyl peroxane and di-butylcyclohexyl peroxydicarbonate, strong di)tert-butylperoxynonane and dicyclohexyl peroxydicarbonate a compound composition, a combination of 2) t-butyl peroxybutane and diisopropyl peroxydicarbonate, a strong two) t-butyl peroxy 7T alkane and a couple A composition obtained by compounding nitrogen diisoheptonitrile, a strong two) tert-butylperoxy 7T alkane and a double ethyl peroxydicarbonate strong ethylhexyl TI, a composition of methyl ethyl ketone peroxide A composition obtained by compounding diphenyl phthalate, p-tert-butylcyclohexyl ester, a composition of methyl ethyl ketone peroxide and dicyclohexyl peroxydicarbonate, methyl ethyl ketone peroxide and diisopropyl peroxydicarbonate a composition obtained by compounding a composition, a composition of methyl ethyl ketone peroxide and azobisisoheptonitrile, a combination of methyl ethyl ketone peroxide and bis(peroxydicarbonate) strong ethyl hexyl TI. One kind. See table for details

 Table strength Φ: Inventive radical polymerization initiator composition is preferably compounded

The radical polymerization initiator composition is selected from the group consisting of azobisisobutyronitrile and di-peroxydicarbonate di-p-tert-butylcyclohexyl ester butyl compound, and dibenzoyl peroxide and oxidation Composition of dicyclohexyl carbonate complex (strong), strong dip) tert-butylperoxy 7T alkane and dicyclohexyl oxydicarbonate complex (strong), methyl ethyl ketone peroxide and oxidized dicarbonate Composition of cyclohexyl ester complex (strong), composition of dodecyl peroxide and diisopropyl peroxydicarbonate (sticky), A composition (~) of a combination of methyl ethyl ketone and azobisisoheptonitrile, a composition of a dodecyl peroxide and a diethylhexyl peroxydicarbonate (root), a tert-butyl peroxybenzoate a composition (root) in which the ester is compounded with diethylhexyl peroxydicarbonate, and a composition (root) in which the dibutylperoxy peroxide and the diethylhexyl peroxydicarbonate are compounded One. Pick

 The above-mentioned low-temperature initiator and high-temperature initiator mass ratio is the same as its n-life, preferably the radical polymerization initiator composition described in the invention, in the preparation of alkenyl ether-butenedioic anhydride Application in copolymers. The mass ratio of the low temperature initiator to the high temperature initiator in the radical polymerization initiator composition is 1:10 to 10:1, preferably 4:1 to 4:1.

 A method for preparing an enol (ester) butenedi anhydride copolymer, comprising the following steps:

 Under the protection of nitrogen, the butyric acid anhydride and the initiator are added to the reaction vessel;

 Add olefin ether (ester), start stirring, and gradually heat up. d «, during the holding period;

 ) raise the temperature to »«, keep warm 3⁄43⁄4· ;

 Recycling excess enamine (ester), the output is the finished product;

 Wherein the initiator is the radical polymerization initiator composition of the present invention. Pick

 The amount of the initiator used is 3⁄4^sw of the total mass of the reaction system. , the preferred amount is the total mass of the system

%. . The total mass of the reaction system refers to the total mass of the butylene anhydride, the initiator and the alkenyl ester. Pick

 The mass ratio of the low temperature initiator to the high temperature initiator in the radical polymerization initiator composition is 1:10 to 10:1, preferably 4:1 to 4:1. Pick

 The ethylenic ether described in the above is a vinyl alkyl ether, a propylene alkyl ether or an alkenyl acetate, and the vinyl alkyl ether is preferably vinyl methyl ether, vinyl ethyl ether or vinyl n-propyl ether. , vinyl isopropyl ether, vinyl n-butyl ether, vinyl isobutyl ether, vinyl tert-butyl ether or vinyl cyclohexyl ether; the propylene alkyl ether is preferably propylene methyl ether, propylene ether, propylene The n-propyl ether or propylene isopropyl ether; the alkenyl acetate is preferably vinyl acetate or acryl acetate. Pick

 Beneficial effects:

In the polymerization, it is necessary to select an initiator having a certain activity or half-life according to the polymerization temperature, so that the radical formation rate and the polymerization rate are moderate. If the initiator activation energy is too high or the half-life is too long, the decomposition rate is too low, which will prolong the polymerization time. However, if the activation energy is too low and the half-life is too short, the initiation is too fast, it is difficult to control the temperature, and it may cause explosion. The polymerization time is prolonged or the initiator is prematurely decomposed, and the polymerization is stopped when the conversion rate is low. Therefore, an initiator having the same half-life or equivalent as the polymerization time should generally be selected. The invention selects the initiation temperature according to the polymerization temperature for preparing the enether (ester) butadiene anhydride copolymer. After the low initiator is combined with the highly stable initiator, the initiation polymerization can be carried out at a lower temperature, and the reaction can be carried out after the heat is released by the polymerization reaction. The use of the radical polymerization initiator composition of the present invention for the preparation of an alkenyl (meth)-maleic anhydride copolymer has the following advantages:

 The low-temperature polymerization time is relatively prolonged, which can reduce the high-temperature polymerization time, which is favorable for the reaction to proceed smoothly;

 However, the total polymerization time is relatively shortened, generally slow, lake, time, low energy consumption; dust

 The slow polymerization is stable, the equipment requirements are relatively reduced, that is, the pressure requirements of the pressure reactor are reduced, the equipment investment is reduced; the dust shifting time is longer, reducing or avoiding the occurrence of side reactions, the obtained product is of good quality, light color, no odor Dust ginseng products have uniform particles, no dust, less risk to workers, and environmentally friendly;

 Not easy to produce explosion, high safety factor; dust

 The viscosity of the product is high and stable (slow Yan ^ »; dust

 The methacrylic anhydride is completely polymerized, no residue; dust

 The closed process is short, and the product is obtained after the monomer is recovered, and the production efficiency is high. Dust

 The preparation method of the enol (ester) butadiene anhydride copolymer provided by the invention has the advantages of simple method, good quality, high safety and environmental friendliness. The product obtained by the method can be widely applied to medicines, oral care products, compound detergents, hand soaps, makeup and toiletries, and can also be used for adhesives and coatings, pesticides, sprays, soil conditioners, latexes. , foam fire extinguishing agents, water treatment, leather tanning and paper industry, etc., can also be used in the processing of waxes and polishing polishes, ceramics, asbestos and steel. dust

/1,

 Earth

Specific real fc^:

Example 1 Dust! Initiator Composition Reference (Cold ») Preparation Dust

 The ruthenium diacetate dicarboxylate ( , , toluene solution, a «storage) was added to the cold » three-necked flask, the dry ice ketone was cooled to one but below, and the † K oxidized dodecanoyl ( ) was slowly added. Homogeneous, transfer refrigeration (see c.), spare. Dust

Example 2 Formulation of the initiator composition cold (shifted)

 ^ m and the mixture is cooled and mixed according to the mass ratio, and the composite initiator is cooled (shifted). Dust

Example 3 Initiator Composition (Cold ») Preparation Dust

 ^ m Example Cold preparation method Dry quality than cold s system. Dust

Example 4 Formulation of the initiator composition but (but »)

ί Ι Refer to the cold preparation method of the example, the dry mass ratio is 7 s. Dust Example 5 Preparation of Initiator Composition Adhesive (Yes)

 The mass ratio of the preparation method which is referred to in the examples is as follows. Prepare

Example 6 Preparation of an Initiator Composition Strong (Adhesive)

 The quality of the preparation method according to the examples was better than that of the paste. Prepare

Example 7 Initiator Composition (Some Preparations)

 The quality ratio of the preparation method according to the embodiment is as follows. Prepare

Example 8 Initiator Composition (Strong Preparation of Strong 3⁄4S)

 According to the preparation method of some of the examples, the mass ratio is 3⁄41. Prepare

Example 9 Preparation of Initiator Composition (Stic)

 Referring to the preparation method of the embodiment, the mass ratio is determined. Prepare

Example 10 Preparation of Copper Alkenyl Methyl Ether Butanediolic Acid Copolymer

 «^ There is a pressure cooker equipped with a thermometer, a stirring slurry, and a pressure gauge, and added with butyl phthalic anhydride (.4). « The initiator is (connected, the example is strong), the reactor is closed, replaced with nitrogen, and then added. Propylene methyl ether (sex I and ), start stirring, heat up to S, heat retention, continue to heat up to different. C, heat preservation, triphenylphosphine detection of non-butenedic acid anhydride (indicating complete reaction of butadiene anhydride), atmospheric distillation, cold trap (strong) collection of boiling point ^ ship. The C fraction was obtained, and the obtained solid was dried to obtain a white powdery solid propylene methyl ether butadiene anhydride copolymer. The yield was in accordance with its intrinsic viscosity. The average molecular weight was 3⁄4 S. Prepare

Example 11 Preparation of vinyl ether butadiene anhydride copolymer

 To an autoclave equipped with a thermometer, a stirring slurry, and a pressure gauge, add butyl phthalic anhydride (.4). « Initiator strong (with type, example), nitrogen replacement, adding refined vinyl ether ('curd), sealed reactor, stirring, temperature rise. C, insulation wins. Then heat up to H, keep warm. Triphenylphosphine is used to detect non-butenedic anhydride (indicating complete conversion of butadiene anhydride), and the boiling point Ϋ Ϋ ϋ fraction is collected by distillation, and the obtained solid is dried to obtain a white powdery solid vinyl ether butadiene hydride copolymer. The yield is in accordance with the intrinsic viscosity of the drunk ether followed by the average molecular weight. Million. Prepare

Example 12 Preparation of copper alkenyl ether butadiene anhydride copolymer

To an autoclave equipped with a thermometer, a stirring slurry, and a pressure gauge, add phthalic anhydride (.4). The mouth initiator is strong (strongly shaped, the examples are supported), replaced with nitrogen, and then added. Propylene ether (different), sealed reactor, start stirring, slowly warm up to understand! C, keep warm, heat up to different. C, insulation has a win, triphenylphosphine detection no Butene dianhydride (indicating complete conversion of butadiene anhydride), atmospheric boiling distillation to collect the boiling point ai fraction, and the obtained solid is dried to obtain a white powdery solid propylene ethyl ether butadiene anhydride copolymer J « plastic, yield iMI Its intrinsic viscosity average molecular weight cylinder «a million. Road

EXAMPLES 13 Alkenyl Acetate Preparation of Butadiene Anhydride Copolymer

 To a dilute autoclave equipped with a thermometer, a stirring slurry, and a pressure gauge, add butyric acid anhydride (plastic is) and plastic 1⁄23 initiator solution (dilute β, Example 备3⁄4), replace with nitrogen, and add «vinyl acetate. Ester (wrap), sealed reactor, open stirring, warm up to ? 3⁄43, Insulation tt, and then heat 63 at 33, Triphenylphosphine to detect non-butenedic anhydride (indicating complete conversion of butadiene anhydride), distilling and collecting boiling point fractions, and drying the obtained solid to obtain white powder Solid vinyl acetate butadiene anhydride copolymer j « tt, the yield of its intrinsic viscosity angle 3⁄4 ^ average molecular weight cylinder ffi7J. Road

EXAMPLES 14 Alkenyl Isopropyl Ether Preparation of Butadiene Anhydride Copolymer

 To a dilute autoclave equipped with a thermometer, a stirring slurry, and a pressure gauge, 3⁄43⁄4 of butyric anhydride (plastic 63), mm initiator release (solution, example jff), nitrogen replacement, and then degummed ethylene Diisopropyl ether (3⁄4 release), sealed reactor, open stirring, warmed to β, heat-resistant Lai plastic, then invented in 33 kinds of plastic, triphenylphosphine detection of non-butenedic anhydride (indicating complete conversion of butadiene anhydride) ), the boiling point of the 3⁄4 iiF ° C fraction is collected by distillation, and the obtained solid is dried to obtain a white powdery solid vinyl isopropyl ether butadiene anhydride copolymer J «plastic, the intrinsic viscosity i«» average molecular weight cylinder. Road

Example 15 Preparation of vinyl n-propyl ether butadiene anhydride copolymer

 To a dilute autoclave equipped with a thermometer, a stirring slurry, and a pressure gauge, add 3⁄43⁄4 of butyric anhydride (plastic 63), a plastic fcffi initiator (thin, Example U), replace with nitrogen, and then add to the plastic. Vinyl n-propyl ether (»), closed reactor, open stirring, heat up to «, heat preservation»3⁄4, and then heat-dissipate 63, triphenylphosphine to detect non-butenedic anhydride (indicating complete conversion of butadiene anhydride), Atmospheric distillation to collect boiling points? The fraction of WTC, the obtained solid is dried to obtain a white powdery solid vinyl n-propyl ether butadiene anhydride copolymer process, yield i1» complex intrinsic viscosity of the molecular cylinder «. Road

Example 16 i-Alkenyl n-butyl ether Preparation of butadiene anhydride copolymer

To a dilute autoclave equipped with a thermometer, a stirring slurry, and a pressure gauge, add 3⁄43⁄4 butyric anhydride (plastic 63), a plastic initiator field (light release angle, routine preparation), replace with nitrogen, and then add the angle β. Vinyl n-butyl ether (plastic), sealed reactor, heated to β, heat preservation »ffi, and then heat-treated at 33, triphenylphosphine to detect non-butenedic anhydride (say The maleic anhydride is completely converted. The boiling point closed fraction is collected by distillation, and the obtained solid is dried to obtain a white powdery solid vinyl n-butyl ether butadiene anhydride copolymer, and the yield is slow. ^^万. Dust Example 17 Preparation of alkenyl methyl ether butenedic anhydride copolymer

 To a cold autoclave equipped with a thermometer, a stirring slurry, and a pressure gauge, add maslinic anhydride (3⁄4 ι )), mm initiator ginseng (cold-cooled type, cold preparation in the examples), and the closed reaction vessel was replaced with nitrogen. Then add '[Mann» vinyl methyl ether (m), turn on the stirring, slowly warm to shift, keep warm », then «insulation} t, triphenylphosphine to detect no phthalic anhydride (indicating butene anhydride) The conversion is complete), the cold trap (shift rc) recovers the vinyl methyl ether, and the obtained solid is dried to obtain a white powdery solid vinyl methyl ether butadiene anhydride copolymer i, and the yield is closed. The average molecular weight is set to w^. Dust

Example 18 Preparation of a copolymer of an alkenyl tert-butyl ether butadiene anhydride copolymer

 To a cold autoclave equipped with a thermometer, a stirring slurry, and a pressure gauge, add a succinimide (3⁄4i ginseng), a mm initiator ginseng (slow ®, 实施 实施 恪), a closed reactor, after nitrogen replacement, Add slow »vinyl tert-butyl ether (slow enthalpy), start stirring, slowly heat up to the application, keep warm, and then keep warm, but triphenylphosphine is tested for no phthalic anhydride (indicating complete conversion of butadiene anhydride) , atmospheric distillation to collect the boiling point i roll. The c fraction is obtained, and the obtained solid is dried to obtain a white powdery solid vinyl tert-butyl ether butadiene anhydride copolymer ι », and the yield of the bottle is intrinsic viscosity slow vine P average molecular weight » 10,000. Dust

Example 19 Preparation of Vinyl Ether Butene Maleic Anhydride Copolymer (Comparative Experiment Cold Dust)

 To a cold autoclave equipped with a thermometer, a stirring slurry, and a pressure gauge, add maslinic anhydride (3⁄4 参 )), mm benzoyl peroxide, replace with nitrogen, add slow » vinyl ether (Jiangxi), and seal the reaction. Kettle, start stirring, heat up «, heat tight, triphenylphosphine monitors no buticic anhydride, distills and collects boiling point slow fraction, and the obtained solid is dried to obtain pale yellow powdery solid 11 gins, the yield is fine «the characteristics Viscosity of viscosity cocci: but ». Dust

Example 20 Preparation of a copolymer of propylene-based methyl ether butadiene anhydride (Comparative experiment

 To a cold autoclave equipped with a thermometer, a stirring slurry, and a pressure gauge, add maslinic anhydride (3⁄4i ginseng), mm, nitrogen replacement, add slow » propylene methyl ether (Jiangxi), seal the reactor, and start stirring. , heating, cold, triphenylphosphine detection of no methic anhydride, distillation to collect the boiling point †» °c fraction, the resulting solid is dried to obtain a pale yellow powdery solid should be», the yield I Congqi its intrinsic viscosity Slow face molecular weight: male title. Dust

Claims

Claim  A radical polymerization initiator composition characterized by comprising a low temperature initiator and a high temperature initiator, wherein the low temperature initiator means a decomposition temperature lower than 60 ° C The high temperature initiator refers to an initiator having a decomposition temperature higher than 70 ° C.  2. The radical polymerization initiator composition according to claim 1, wherein the low temperature initiator is selected from the group consisting of dicycloethyl peroxydicarbonate, azobisisoheptanenitrile, and diperoxydicarbonate. One of 2-ethylhexyl)ester, di(p-butylcyclohexyl peroxydicarbonate), diisopropyl peroxydicarbonate, the high temperature initiator selected from the group consisting of dodecanoyl peroxide and azo One of diisobutyronitrile, dibenzoyl peroxide, tert-butyl peroxybenzoate, 2,2-di(tert-butylperoxy)butane, methyl ethyl ketone peroxide. The radical polymerization initiator composition according to claim 2, wherein the radical polymerization initiator composition is selected from the group consisting of dodecanoyl peroxide and di(p-butylcyclohexyl peroxydicarbonate). a combination of a composition, a composition of dodecyl peroxide and dicyclohexyl peroxydicarbonate, a combination of dodecyl peroxide and diisopropyl peroxydicarbonate a composition obtained by compounding dodecyl peroxide with azobisisoheptonitrile, a combination of dodecyl peroxide and bis(2-ethylhexyl) peroxydicarbonate, a composition obtained by compounding nitrogen diisobutyronitrile with di(p-butylcyclohexyl peroxydicarbonate), a combination of azobisisobutyronitrile and dicyclohexyl peroxydicarbonate, and even A composition obtained by compounding nitrogen diisobutyronitrile with diisopropyl peroxydicarbonate, a combination of azobisisobutyronitrile and azobisisoheptonitrile, azobisisobutyronitrile and A composition of bis(2-ethylhexyl) peroxydicarbonate, dibenzoyl peroxide and diperoxydicarbonate (p-tert-butyl) a composition obtained by compounding hexyl ester, a combination of dibenzoyl peroxide and dicyclohexyl peroxydicarbonate, dibenzoyl peroxide and diisopropyl peroxydicarbonate The composition, the composition of dibenzoyl peroxide and azobisisoheptanonitrile, and the combination of dibenzoyl peroxide and bis(2-ethylhexyl)peroxydicarbonate Composition, a combination of tert-butyl peroxybenzoate and di(p-butylcyclohexyl peroxydicarbonate), tert-butyl peroxybenzoate and dicyclohexyl peroxydicarbonate The compound composition, the composition of the t-butyl peroxybenzoate and the diisopropyl peroxydicarbonate, the t-butyl peroxybenzoate and the azobisisoheptonitrile are combined. Composition, a combination of tert-butyl peroxybenzoate and bis(2-ethylhexyl) peroxydicarbonate, 2,2-di(tert-butylperoxy)butane and peroxidation A combination of di(n-butylcyclohexyl) dicarbonate, 2,2-di(tert-butylperoxy)butane and dicyclohexyl peroxydicarbonate a composition of 2,2-di(tert-butylperoxy)butane and diisopropylperoxydicarbonate, 2,2-di(tert-butylperoxy)butane and azodi A composition obtained by compounding isoheptonitrile, a composition of 2,2-di(tert-butylperoxy)butane and bis(2-ethylhexyl)peroxydicarbonate, methyl ethyl ketone peroxide a composition obtained by compounding diperoxydicarbonate di(p-butylcyclohexyl ester), a combination of methyl ethyl ketone peroxide and dicyclohexyl peroxydicarbonate, A composition obtained by compounding methyl ethyl ketone with diisopropyl peroxydicarbonate, a composition of methyl ethyl ketone peroxide and azobisisoheptonitrile, a methyl ethyl ketone peroxide and a double bisphosphonate (2-B) One of the compositions in which the hexyl hexyl ester is compounded. The radical polymerization initiator composition according to claim 3, wherein the radical polymerization initiator composition is selected from the group consisting of azobisisobutyronitrile and di(n-butylcyclohexyl)peroxycarbonate. a compound composition, a composition of dibenzoyl peroxide and dicyclohexyl peroxydicarbonate, 2,2-di(tert-butylperoxy)butane and diperoxydicarbonate Composition of cyclohexyl ester complex, composition of methyl ethyl ketone peroxide and dicyclohexyl peroxydicarbonate, composition of dodecyl peroxide and diisopropyl peroxydicarbonate, methyl ethyl ketone peroxide Composition compounded with azobisisoheptanenitrile, composition of dodecyl peroxide and bis(2-ethylhexyl)peroxydicarbonate, tert-butyl peroxybenzoate and peroxydicarbonate a composition of bis(2-ethylhexyl) ester complex, a composition of 2,2-di(tert-butylperoxy)butane and bis(2-ethylhexyl)peroxydicarbonate One.  The radical polymerization initiator composition according to any one of claims 1 to 4, wherein the mass ratio of the low temperature initiator to the high temperature initiator is 1:10 to 10:1, preferably 4: 1~4: 1.  Use of the radical polymerization initiator composition according to any one of claims 1 to 4 for the preparation of an alkenyl (meth)-butenedioic acid anhydride copolymer.  7. A method for preparing an enol (ester)-butenedic anhydride copolymer, comprising the steps of:  A) adding butadiene anhydride and initiator to the reaction vessel under nitrogen protection;  B) Add the enol (ester), start stirring, gradually heat to 35~60 °C, keep l~5h;  C) The temperature is raised to 65~85 °C, and the temperature is kept for l~2h;  D) recovering excess enamine (ester), which is the finished product; The initiator is the radical polymerization initiator composition according to any one of claims 1 to 4.  The process for producing an enol (ester)-butenedic anhydride copolymer according to claim 7, wherein the free radical polymerization initiator composition is used in an amount of from 0.1 to 10.0% by mass based on the total mass of the reaction system. Preferably, it is 0.5 to 1.5%. .  The method for producing an enol (ester)-butenedic anhydride copolymer according to claim 7, wherein the mass ratio of the low temperature initiator to the high temperature initiator in the radical polymerization initiator composition is 1 : 10 to 10: 1, preferably 4: 1 to 4: 1. 10. The process for preparing an enol (ester)-butenedic anhydride copolymer according to claim 7, wherein the alkenyl ether is a vinyl alkyl ether, a propylene alkyl ether or an alkene. Acetyl acetate, the vinyl alkyl ether is preferably vinyl methyl ether, vinyl ethyl ether, vinyl n-propyl ether, vinyl isopropyl ether, vinyl n-butyl ether, vinyl isobutyl ether, vinyl tert-butyl Ether or vinyl cyclohexyl ether; the propylene alkyl ether is preferably propylene methyl ether, propylene ether, propylene n-propyl ether or propylene The propyl ether; the alkenyl acetate is preferably vinyl acetate or acryl acetate ₍