CN1309751C - Modified coupling agent and its preparing process and use - Google Patents
Modified coupling agent and its preparing process and use Download PDFInfo
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- CN1309751C CN1309751C CNB2003101168177A CN200310116817A CN1309751C CN 1309751 C CN1309751 C CN 1309751C CN B2003101168177 A CNB2003101168177 A CN B2003101168177A CN 200310116817 A CN200310116817 A CN 200310116817A CN 1309751 C CN1309751 C CN 1309751C
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- maleic anhydride
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Abstract
The present invention provides a coupling agent for filling and modifying organic polymers and a preparing method thereof. The coupling agent utilizes maleic anhydride and polyisobutylene to graft under the action of initiating agents and without the action of the initiating agents to prepare maleic anhydride grafting polyisobutylene polymers, and the grafting ratio can be controlled within the range of 1 to 80%. The molecular weight of the polyisobutylene is 800 to 10000 of common polyisobutylene or high activity polyisobutylene, the grafting reaction temperature is from 120 to 250 degrees, and the reaction time is from 30 to 240 minutes. The prepared coupling agent can effectively improve the compatibility and the adhesive force of organic polymers and inorganic fillers, and has the advantages of no pollution, accurate grafting ratio control, wide range of application, etc.
Description
Technical field
The present invention relates to a kind of maleic anhydride and polyisobutene of utilizing, carry out graft polymerization reaction under the effect of initiator or no initiator, preparation can be used for the filling-modified maleic anhydride graft polyolefin polymerization compound coupling agent of organic polymer.
Background technology
Have nonpolar and crystalline organic polymer, very poor with other materials as consistencies such as polar polymer, inorganic fillers, can't prepare useful intermingling material.In order to make matrix material reach the performance of expection, need to use coupling agent carry out modification, to strengthen the consistency and the bonding force of it and basic resin to the weighting material surface.Coupling agent is to improve plastic products quality class, raising plastics added value, promotion plastics new product development and The application of new technique to the effect of weighting material interface modification.
Maleic anhydride and polyolefin graft polymers all are widely used at aspects such as blend polymer, polymer/inorganic weighting material, polymkeric substance/organic fibre, composite reinforcing material and binding agents as coupling agent.The method for preparing the maleic anhydride graft polyolefin polymer at present both at home and abroad has scorification, solution method, radiation method and solid phase method, and wherein most important method is a scorification.Fusion-grafting can carry out in single screw extrusion machine, twin screw extruder or Brabender rheometer.For example set forth among the CN1230554 with polypropylene, maleic anhydride, initiator and other additives, uniform mixing under the help of paucidisperse agent, then mixture is added in the forcing machine hopper and melt extrudes, but the product that obtains all exist maleic anhydride residual quantity height, crosslinked serious, percentage of grafting control is inaccurate, the problem of mobile difference.Though add cross-linked inhibitor by adopting, the method for oxidation inhibitor or employing mixed initiator is played a role, and effect is also not obvious.
In high carbon acid calcium filled polypropylene, poly project, requiring calcium carbonate-filled amount is 50%, selects various coupling agents such as titanic acid ester etc. for use, and the loading level of lime carbonate can only reach 30%, and performance index do not reach requirement yet, fails at present to solve always.
Summary of the invention
The object of the invention is to propose with the technical scheme of maleic anhydride graft polyisobutene polymkeric substance as coupling agent, make calcium carbonate-filled amount meet and exceed 50%, and adopt that a kind of simple and feasible method obtains that pollution-free (the maleic anhydride residual quantity is very low), degree of crosslinking are low, good fluidity, percentage of grafting control accurate maleic anhydride graft polyisobutene polymkeric substance coupling agent.
The inventive method is that maleic anhydride and polyisobutene are added in the reactor of band stirring; it is even to add stirring solvent, adds initiator or do not add initiator under nitrogen protection, carries out graft reaction; temperature of reaction is 120～250 ℃, successive reaction 30～240 minutes.Carry with nitrogen gas then and remove unreacted maleic anhydride, reclaim solvent, obtain maleic anhydride graft polyisobutene polymkeric substance coupling agent product at last.
Polyisobutene of the present invention is the common polyisobutene or the high-activity polyisobutene of molecular weight 800～10000.High-activity polyisobutene requires end alkene content greater than 60%, and preferred 70～90%.
Solvent of the present invention can be selected benzene,toluene,xylene, ethyl acetate, acetone, butanone, methylethylketone, chloroform, propyl carbinol for use and not have aromatic hydrocarbon solvent.Solvent load is 10～80% (weight) of polyisobutene amount, preferred 30～50%.
Initiator of the present invention can be selected alkyl peroxide, ester class superoxide and acyl class superoxide for use, preferably dicumyl peroxide, benzoyl peroxide, propionic acid acid amides, stearylamide, tert-butyl peroxide, ditertiary butyl peroxide, tert-butyl peroxide trimethylacetic acid ester, Diisopropyl azodicarboxylate, 2,3-dimethyl-2,3-diphenyl butane, peroxidized t-butyl perbenzoate.The mixture of one or more materials in dicumyl peroxide, benzoyl peroxide, ditertiary butyl peroxide, the tert-butyl peroxide trimethylacetic acid ester most preferably.
Temperature of reaction of the present invention is 120～250 ℃, preferred 150～200 ℃.This temperature range is one of key of the present invention.Temperature of reaction is lower than 120 ℃, and reaction conversion ratio is low; Temperature of reaction is higher than 250 ℃, and maleic anhydride and polyisobutene will speed up decomposition.
Reaction times of the present invention is 30～240 minutes, preferred 90～120 minutes.
The molar ratio of initiator of the present invention and maleic anhydride is 1: 8～15, preferred 1: 10～12.
The mol ratio of maleic anhydride of the present invention and polyisobutene is 1: 1～8, preferred 1: 3～5.
The maleic anhydride graft polyisobutene polymkeric substance coupling agent of the present invention preparation, its percentage of grafting controlled range be 1～80%, and be preferred 2～40%, and most preferably 5～20%.
Organic polymer of the present invention can be polyvinyl chloride, polyethylene, polypropylene, polystyrene, ethylene-propylene copolymer, ethene-vinyl acetate copolymer, engineering plastics, polyester, nylon, rubber, Resins, epoxy, resol, unsaturated polyester.
Weighting material of the present invention can be lime carbonate, glass, talcum, natural Calucium Silicate powder, mica, kaolin, silicon-dioxide, titanium dioxide, red mud, flyash, diatomite, glass microballon, barium sulfate (calcium), silica powder, the tremolite, aluminum oxide, wollastonite, carbon black, silica-alumina carbon black, brucite.
Maleic anhydride graft polyisobutene polymkeric substance is because its structural characteristics, it is a kind of good long-chain coupling agent that contains side chain, polyisobutene part in the maleic anhydride graft polyisobutene polymkeric substance is good with the resin compatible of infill system, and can form intermolecular entanglement, carboxylic group and weighting material form complexing or ionic linkage chemical action, help improving the combination between weighting material and the polymeric matrix, can significantly improve the performance such as tensile strength, shock strength, rigidity, heat-drawn wire, processing fluidity of system, be a kind of new and effective coupling agent.Product is through experimental applications, and calcium carbonate-filled amount meets and exceeds 50%, and every performance index also reach requirement fully.
Embodiment
Following example is to further specify of the present invention, rather than limits the scope of the invention.
Embodiment 1～3rd, the preparation of high-activity polyisobutene grafted maleic anhydride under the no initiator condition.
Embodiment 1
With 1000 gram end alkene content is that 70% high-activity polyisobutene (molecular weight 2300) adds in the reactor of band stirring, behind nitrogen replacement, 1: 5 ratio of mol ratio in maleic anhydride and polyisobutene adds 0.8 gram maleic anhydride, toluene 300ml, mixing stirs, at speed setting is 600rpm, and temperature of reaction is under 180 ℃ the condition, to react 200 minutes.Carry 50 minutes at 190 ℃ with nitrogen gas at last, remove unreacted maleic anhydride, reclaim solvent xylene, obtain maleic anhydride graft polyisobutene polymkeric substance coupling agent.
Prepared reactant is placed vacuum drying oven under 110 ℃ temperature dry 24 hours, removes the maleic anhydride monomer that has neither part nor lot in graft reaction, guarantee in the grafts may partial hydrolysis anhydride group be reduced into the form of cyclic anhydride base.Take out 1～2g sample from dried reactant, be placed on heating for dissolving in the xylene solution of 150ml, the NaOH ethanolic soln with 0.1M after 4 hours carries out titration to it, surveys its percentage of grafting.The results are shown in Table 1.
Embodiment 2
With 1000 gram end alkene content is that 71% high-activity polyisobutene (molecular weight 1300) adds in the reactor of band stirring, behind nitrogen replacement, 1: 5 ratio of mol ratio in maleic anhydride and polyisobutene adds 1.5 gram maleic anhydrides, dimethylbenzene 300ml, mixing stirs, at speed setting is 600rpm, and temperature of reaction is under 180 ℃ the condition, to react 200 minutes.Carry with nitrogen gas and to remove unreacted maleic anhydride, reclaim solvent, obtain maleic anhydride graft polyisobutene polymkeric substance coupling agent, adopt the volumetry identical to survey its percentage of grafting with example 1.The results are shown in Table 1.
Embodiment 3
With 1000 gram end alkene content is that 69% high-activity polyisobutene (molecular weight 900) adds in the reactor of band stirring, behind nitrogen replacement, 1: 5 ratio of mol ratio in maleic anhydride and polyisobutene adds 2.2 gram maleic anhydrides, benzene 300ml, mixing stirs, at speed setting is 600rpm, and temperature of reaction is under 180 ℃ the condition, to react 200 minutes.Carry with nitrogen gas and to remove unreacted maleic anhydride, reclaim solvent, obtain maleic anhydride graft polyisobutene polymkeric substance coupling agent, adopt the volumetry identical to survey its percentage of grafting with example 1.The results are shown in Table 1.
From table 1, can see, need not initiator, just can obtain that pollution-free (the maleic anhydride residual quantity is very low), degree of crosslinking are low, good fluidity, percentage of grafting control accurate maleic anhydride graft polyisobutene polymkeric substance coupling agent for high-activity polyisobutene.
Embodiment 4～5th, the preparation of common polyisobutene grafted maleic anhydride under the initiator effect.
Embodiment 4
The 1000 common polyisobutene of gram (molecular weight 2300) are added in the reactor of band stirring, behind nitrogen replacement, 1: 5 ratio of mol ratio in maleic anhydride and polyisobutene adds 0.8 gram maleic anhydride, acetone 300ml, the mixing that stirs adds the initiator ditertiary butyl peroxide, is 600rpm at speed setting, temperature of reaction is under 180 ℃ the condition, to react 120 minutes.Carry 50 minutes at 190 ℃ with nitrogen gas at last, remove unreacted maleic anhydride, reclaim solvent, obtain maleic anhydride graft polyisobutene polymkeric substance coupling agent, adopt the volumetry identical to survey its percentage of grafting with example 1.The results are shown in Table 1.
Embodiment 5
The 1000 common polyisobutene of gram (molecular weight 1300) are added in the reactor of band stirring, behind nitrogen replacement, 1: 5 ratio of mol ratio in maleic anhydride and polyisobutene adds 1.5 gram maleic anhydrides, propyl carbinol 300ml, the mixing that stirs adds the initiator ditertiary butyl peroxide, is 600rpm at speed setting, temperature of reaction is under 180 ℃ the condition, to react 120 minutes.Nitrogen gas is carried and is removed unreacted maleic anhydride, reclaims solvent, obtains maleic anhydride graft polyisobutene polymkeric substance coupling agent, adopts the volumetry identical with example 1 to survey its percentage of grafting.The results are shown in Table 1.
From table 1, can see, common polyisobutene is grafted maleic anhydride under action of evocating, can obtain also that pollution-free (the maleic anhydride residual quantity is very low), degree of crosslinking are low, good fluidity, percentage of grafting control accurate maleic anhydride graft polyisobutene polymkeric substance coupling agent.
Embodiment 6～7th, utilize maleic anhydride graft polyisobutene polymkeric substance coupling agent that the present invention prepares with calcium carbonate-filled application in organic polymer.Comparative Examples 1～2nd utilizes titanate coupling agent with calcium carbonate-filled application contrast in organic polymer.
Embodiment 6
Maleic anhydride graft polyisobutene polymkeric substance coupling agent, lime carbonate, polyethylene 2200J, the oxidation inhibitor 168/1076 of the present invention's preparation were pressed 1.5: 30: 68.5: after 0.05 part by weight (wt%) is composite, in high-speed mixer, high-speed stirring is 3 minutes under the normal temperature, send in the twin screw extruder again, processing temperature is 200 ℃, through melt extruding, after the granulation, drying, compressing tablet, pressing GB1040 test tensile property, GB1043 tests impact property.The results are shown in Table 2.
Comparative Examples 1
Coupling agent titanic acid ester, lime carbonate, polyethylene 2200J, oxidation inhibitor 168/1076 were pressed 1.5: 30: 68.5: after 0.05 part by weight (wt%) is composite, in high-speed mixer, high-speed stirring is 3 minutes under the normal temperature, send in the twin screw extruder again, processing temperature is 200 ℃, through melt extruding, after the granulation, drying, compressing tablet, pressing GB1040 test tensile property, GB1043 tests impact property.The results are shown in Table 2.
Embodiment 7
Maleic anhydride graft polyisobutene polymkeric substance coupling agent, lime carbonate, polypropylene T30S, the oxidation inhibitor 168/1076 of the present invention's preparation were pressed 1.5: 30: 68.5: after 0.05 part by weight (wt%) is composite, in high-speed mixer, high-speed stirring is 3 minutes under the normal temperature, send in the twin screw extruder again, processing temperature is 200 ℃, through melt extruding, after the granulation, drying, compressing tablet, pressing GB1040 test tensile property, GB1043 tests impact property.The results are shown in Table 2.
Comparative Examples 2
Coupling agent titanic acid ester, lime carbonate, polypropylene T30S, oxidation inhibitor 168/1076 were pressed 1.5: 30: 68.5: after 0.05 part by weight (wt%) is composite, in high-speed mixer, high-speed stirring is 3 minutes under the normal temperature, send in the twin screw extruder again, processing temperature is 200 ℃, through melt extruding, after the granulation, drying, compressing tablet, pressing GB1040 test tensile property, GB1043 tests impact property.The results are shown in Table 2.
From embodiment 6,7 and Comparative Examples 1, as can be seen, use maleic anhydride graft polyisobutene polymkeric substance coupling agent to compare with titanate coupling agent in 2, every indexs such as calcium carbonate-filled rate, elongation at break, tensile strength, shock strength all have significant improvement.
Table 1
| Example | The mol ratio of maleic anhydride and polyisobutene | The polyisobutene molecular weight | Initiator | Percentage of grafting |
| 1 | 1∶5 | 2300 | Do not have | 2.7％ |
| 2 | 1∶5 | 1300 | Do not have | 3.5％ |
| 3 | 1∶5 | 900 | Do not have | 5.1％ |
| 4 | 1∶5 | 2300 | Ditertiary butyl peroxide | 1.5％ |
| 5 | 1∶5 | 1300 | Ditertiary butyl peroxide | 2.1％ |
Table 2
| Lime carbonate wt% | Organic polymer | Coupling agent | Elongation at break % | Tensile strength MPa | Shock strength | |
| Example 6 | 50 | PE 2200J | The present invention | 300 | 26 | 32KJ/m 2(simply supported beam) |
| Comparative Examples 1 | 30 | PE 2200J | Titanic acid ester | 90 | 20 | 15KJ/m 2(simply supported beam) |
| Example 7 | 50 | PP T30S | The present invention | 300 | 28 | 280J/m (socle girder) |
| Comparative Examples 2 | 30 | PP T30S | Titanic acid ester | 85 | 19 | 130J/m (socle girder) |
Claims (10)
1; a kind of preparation method of modification coupling agent; it is characterized in that: by maleic anhydride and polyisobutene are added in the reactor of band stirring; it is even to add stirring solvent; under nitrogen protection, add initiator or do not add initiator; under 120～250 ℃ of temperature; carried out graft reaction continuously 30～240 minutes; use nitrogen then; gas is carried, and removes unreacted maleic anhydride, reclaims solvent; obtain maleic anhydride graft polyisobutene polymkeric substance coupling agent at last; the mol ratio of maleic anhydride and polyisobutene is 1: 1～8, and the mol ratio of initiator and maleic anhydride is 1: 8～15, and its percentage of grafting span of control is 1～80%.
2, according to the preparation method of a kind of modification coupling agent described in the claim 1, it is characterized in that: polyisobutene is the common polyisobutene or the high-activity polyisobutene of molecular weight 800～10000, and high-activity polyisobutene requires end alkene content to be not less than 60%.
3, according to the preparation method of a kind of modification coupling agent described in the claim 1, it is characterized in that: solvent can be selected benzene,toluene,xylene, ethyl acetate, acetone, butanone, methylethylketone, chloroform, propyl carbinol for use or not have aromatic hydrocarbon solvent, and solvent load is 10～80% of a polyisobutene weight.
4, according to the preparation method of a kind of modification coupling agent described in the claim 1, it is characterized in that: initiator can be selected alkyl peroxide, ester class superoxide or acyl class superoxide for use.
5, according to the preparation method of a kind of modification coupling agent described in the claim 1, it is characterized in that: initiator can be selected dicumyl peroxide, benzoyl peroxide, propionic acid acid amides, stearylamide, tert-butyl peroxide, ditertiary butyl peroxide, tert-butyl peroxide trimethylacetic acid ester, Diisopropyl azodicarboxylate, 2 for use, 3-dimethyl-2,3-diphenyl butane, peroxidized t-butyl perbenzoate.
6, according to the preparation method of a kind of modification coupling agent described in the claim 1, it is characterized in that: the mol ratio of maleic anhydride and polyisobutene is 1: 3～5, and the molar ratio of initiator and maleic anhydride is 1: 10～12.
7, according to the preparation method of a kind of modification coupling agent described in the claim 1, it is characterized in that: maleic anhydride graft polyisobutene polymkeric substance coupling agent, its percentage of grafting controlled range is 5～20%.
8, the purposes of the coupling agent of the preparation method of a kind of modification coupling agent according to claim 1 preparation, it is characterized in that: it is filling-modified that it is used for organic polymer.
9, the purposes of a kind of modification coupling agent described in according to Claim 8, it is characterized in that: organic polymer can be polyvinyl chloride, polyethylene, polypropylene, polystyrene, ethylene-propylene copolymer, ethene-vinyl acetate copolymer, polyester, nylon, rubber, Resins, epoxy, resol or unsaturated polyester.
10. a kind of purposes with the modification coupling agent described in according to Claim 8, it is characterized in that: weighting material can be lime carbonate, glass, talcum, mica, kaolin, silicon-dioxide, titanium dioxide, red mud, flyash, diatomite, glass microballon, barium sulfate, calcium sulfate, silica powder, the tremolite, aluminum oxide, wollastonite, carbon black, silica-alumina carbon black or brucite.
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