CN101955592A - Method for preparing thermo-plastically reprocessed cross-linked halogenated butyl rubber - Google Patents
Method for preparing thermo-plastically reprocessed cross-linked halogenated butyl rubber Download PDFInfo
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Abstract
The invention relates to a method for preparing a thermo-plastically reprocessed cross-linked halogenated butyl rubber. A rubber is cross-linked by blending a polymer containing a pyridine side group or dicyclopentadiene formate thermally-reversible cross-linking agent and a halogenated butyl rubber and performing quaternization or esterification on the mixture under a thermo-compression condition. The cross-linked rubber sample is subjected to reverse quaternization or reverse Diels-Alder reaction of dicyclopentadiene cross-linking bridge bonds under the thermo-compression condition at a high temperature to perform decrosslinking, so the cross-linked rubber has thermoplastic processability. The rubber sample cross-linked by the thermally-reversible cross-linking agent has the performance of a vulcanized rubber and thermoplastic processability, so that rubber scraps and waste or old rubber products are conveniently reprocessed and utilized.
Description
Technical field
The present invention relates to a kind of hot reversible crosslink technology of halogen functionalized rubber, particularly a kind of halogenated butyl rubber with contain tertiary amine polymer or the crosslinking technological of dicyclopentadiene diformate linking agent and the performance of cross-linked rubber.
Background technology
Halogenated butyl rubber not only has excellent resistance to air loss and good thermotolerance, ageing resistance and anti-behaviour of ozone, also have advantages such as vulcanization rate is fast, good with other rubber compatibilities, mutual viscosity is good, compression set is little, it is had a wide range of applications in medical sealing article, tube or fields such as tire liner, protective clothing.
As everyone knows, rubber has the chemically crosslinked network after by all kinds of vulcanizing agent vulcanization crosslinkings, thereby possesses certain physical mechanical property and some other necessary performance.But, the chemical crossbond of cross-linked rubber inside causes it can not carry out the secondary processing moulding, this just makes that a large amount of leftover bits and waste product are difficult to obtain to utilize once again to waste by the thermoplastic working method, seek a kind ofly both can keep traditional vulcanized rubber structure and physical and mechanical properties, can carry out the flow crosslinking technological of processing of thermoplastic again, be expected to make rubber to have cured properties concurrently and can repeat processibility.Utilizing thermal-reversible cross-linking agent to realize the halogenated butyl rubber reversible crosslink is basic ideas of the present invention, and the concrete hot reversible reaction of adopting has following two kinds.
(1) based on the THERMALLY REVERSIBLE COVALENT system of the reversible Diels-Alder cycloaddition reaction of heat
Contain the bifunctional vinyl compound of conjugated double bond and the Diels-Alder cycloaddition reaction of double bond containing close bifunctional vinyl compound generation and have thermal reversibility, this reaction can be used for the hot reversible crosslink of polymkeric substance.
1969, United States Patent (USP) (USP3435033) has been reported to contain the polymer of furan group on saturated main chain, with the bismaleimides is linking agent, adopt the method for polymers soln cross-linking reaction to make hot reversible crosslink polymkeric substance, can soften moulding during this polymkeric substance heating, softening temperature is 120-140 ℃.The crosslinked reaction by furans and maleimide generation D-A wherein forms, as shown in Equation 1:
Formula 1 contains the D-A reaction and the reversed reaction thereof of furan group polymer and bismaleimides
The hot reciprocal characteristics of separating dimerization (formula 2) of dicyclopentadiene (DCPD) when utilizing the cycloaddition dimerization of cyclopentadiene under the room temperature state (CPD) and high temperature, CPD is introduced the macromolecular chain side group, can realize hot reversible crosslink by the hot reversible dimerization between the side group CPD.
The D-A reaction and the reversed reaction thereof of formula 2 cyclopentadiene
The Japanese Patent of Harumi in 1973 (JP73-36293) has reported by cyclopentadiene sodium (CPDNa) and the polymer reaction that contains the Cl side group and has obtained with the crosslinked polyvinyl chloride of DCPD (PVC), chloroprene rubber (CR) and Hydrin (PECH) that these cross-linked polymers all have hot reversible feature.
(USP4138441) such as Kennedy of the U.S. in 1979 is by dimethyl cyclopentadienyl aluminium (Me
2AlCPD) carry out permutoid reaction with chlorine-containing polymer, made the chlorinated butyl rubber and chlorination second third glue that have the CPD side group, their solubility behavior proves: product crosslinked really by due to the CPD side group dimerization.The glue sample that makes all presents the thermoplasticity flowability twice in 150 ℃, 170 ℃ mold pressings.
1985, (Masatoshi M, Fumihiko A, Toshio U such as Masatoshi, Yasuhiro.I:Kuniharu, N.Makromol.Chem.1985,186:473) having synthesized side group is the chloromethylated polystyrene of CPD, and product is dissolved in oil of mirbane, behind 50 ℃ of heating 1h, crosslinked polymer, be heated to 230 ℃ after dissolving again, made the polystyrene of hot reversible crosslink.
Chen Xiaonong etc. have synthesized dicyclopentadiene dioctyl phthalate (China Synthetic Rubber Industry, 1996,19 (3): 159), its sylvite has been studied the crosslinking reaction of chlorine-containing polymer solution, (J.Polym.Sci.Polym.Chem.1999,37:4390 as linking agent; J.Polym.Sci.Polym.Chem.2000 38:1662), and has investigated the hot reversible crosslink characteristic of gained cross-linked polymer.In addition, dicyclopentadiene diformate and epichlorohydrin reaction are made the DCPD derivative of being with the bis-epoxy base, ring-opening copolymerization by this derivative and oxyethane, propylene oxide obtain hot reversible crosslink polyethers thermoplastic elastomer (the polymer journal, 2000,6:696).
The present invention mixes as thermal-reversible cross-linking agent the dicyclopentadiene diformate with halogenated butyl rubber, the halogenated butyl rubber of Inorganic Fillers Filled is implemented hot reversible crosslink.The advantage of this linking agent is that carboxylate salt is the group of high reaction activity, good stability, and chance water, air do not decompose, and be with the crosslinking reaction mild condition of rubber, directly crosslinked with implementing in its method adding rubber with blend.
(2) the THERMALLY REVERSIBLE COVALENT system of reacting based on the reversible Menschutkin of heat
Menschutkin reaction is the reaction between halohydrocarbon and the tertiary amine compound, i.e. quaterisation, and this reaction also has thermal reversibility.
(J.Polym.Sci.Polym.Chem.2000 such as Xiaonong Chen, 38:4373), crosslinked polymkeric substance will be obtained behind two kinds of emulsion co-coagulations by emulsion polymerization synthesizing propylene acid butyl ester-vinylbenzene-p-chloromethyl styrene (PBSC) copolymer emulsion and styrene-propene acid dimethylamine ethyl ester (PSN) copolymer emulsion.This cross-linked polymer can be at 215 ℃ through the hot pressing reshaping.
The present invention then is that the polymkeric substance that will contain tertiary amine mixes with halogenated butyl rubber as thermal-reversible cross-linking agent, and the halogenated butyl rubber of Inorganic Fillers Filled is implemented hot reversible crosslink.
Summary of the invention
The purpose of this invention is to provide the method for halogenated butyl rubber that a kind of preparation has the Inorganic Fillers Filled of hot reversible crosslink characteristic.Replace traditional linking agent (vulcanizing agent) that rubber is implemented covalent cross-linking with thermal-reversible cross-linking agent, when guaranteeing that cross-linked rubber possesses certain physical and mechanical property, give its thermoplasticity processibility, reclaim and a multiplexing difficult problem to solve rubber scrap stock and waste product, improve resource utilization, reduce the cost of goods.
The present invention implements hot THERMALLY REVERSIBLE COVALENT by two kinds of methods to halogenated butyl rubber.
(1) utilize the dicarboxylate derivative of dicyclopentadiene as linking agent, halogenated butyl rubber to Inorganic Fillers Filled carries out crosslinked, that is: the linking agent carboxylate groups with contain reactive halogen generation esterification on the halogenation isoprene-isobutylene rubber molecular chain, acquisition has the isoprene-isobutylene rubber of DCPD bridged bond cross-linked network, and dicyclopentadiene structure wherein provides hot reciprocal characteristics.As shown in Equation 3.
Esterification and contrary DA reaction thereof between formula 3 dicyclopentadiene diformates and polymer containing halogen molecular chain (X=Br or Cl, M=K or Na,
)
(2) polymkeric substance that will contain the pyridine side group is as linking agent, the halogenated butyl rubber of Inorganic Fillers Filled is carried out crosslinked, as shown in Equation 4.
Formula 4 quaternized crosslinking reactions are conciliate the crosslinking reaction formula
Contain the preparation of pyridine side group polymeric crosslinker
Contain pyridine side group polymeric crosslinker and adopt the method for emulsion polymerization preparation.Polymerization is adopted, and to contain the pyridyl monomer be one or more combination in the following material: 2-chloro-4-allyl pyridine, 4-vinylpridine, 2-vinyl pyridine and 4-stibazole etc.The NOT-function monomer that adopts comprises: (1) acrylate monomer, for example methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, butyl acrylate, butyl methacrylate, vinylformic acid isopentyl ester, Octyl acrylate; (2) vinyl monomer, for example vinylbenzene, vinyl toluene.Regulate the composition of linking agent by these monomeric proportionings.
Initiator that polymerization is adopted is a water soluble starter, as Potassium Persulphate, ammonium persulphate etc., emulsifying agent is anionic, non-ionic type or their composition, as the condenses (OP-10) of sodium laurylsulfonate, sodium lauryl sulphate, polyvinyl alcohol or sim alkylphenol and oxyethane.
The letex polymerization prescription is (mass percent): vinylbenzene 10%-60%, and acrylate 5%-40%, pyridine functional monomer 5%-30%, initiator 0.5%-10.0%, emulsifying agent 1%-10%, pH buffer reagent 0.5%-2.0%, surplus is a deionized water.
The preparation process that contains pyridine side group polymeric crosslinker: partial monosomy mixture, emulsifying agent, pH regulator agent and deionized water are added in the reactor, and the pre-emulsification of normal temperature makes pre-emulsion under nitrogen protection and mechanical stirring condition.Pre-emulsion is heated to 40-90 ℃, adds the aqueous solution initiated polymerization of initiator, drip monomer mixture again, drip time 1-5h, react 6-18h after dropwising again, cooling discharging obtains the linking agent emulsion.To obtain polymeric crosslinker after the emulsion breaking drying.
The preparation of dicyclopentadiene diformate linking agent
Produce cyclopentadiene by the dicyclopentadiene thermo-cracking, collect 41 ℃ of cuts.Sodium sand is added in the anhydrous tetrahydro furan, under stirring and ice-water bath cooling conditions, drip cyclopentadiene.Behind the reaction 24h, gained cyclopentadiene sodium solution is mixed with excessive dry ice, react 6h, obtain dicyclopentadiene sodium diformate slurry, obtain dicyclopentadiene sodium diformate pressed powder after removing solvent, be sodium salt crosslinked dose.The dicyclopentadiene sodium diformate is obtained the dicyclopentadiene dioctyl phthalate with the hydrochloric acid neutralization, obtain the dicyclopentadiene Potassium hydrogen diformate with the potassium hydroxide neutralization again, be the sylvite linking agent.
The hot reversible crosslink of halogenated butyl rubber
With institute of the present invention synthetic thermal-reversible cross-linking agent and rubber by predetermined prescription in the mill about mixing 25min, mixing even back is sheet down, room temperature is placed 24h, makes reversible crosslink glue sample in 170-180 ℃ of compression molding then on vulcanizing press.
Base rubber is a halogenated rubber among the present invention, for example brominated butyl rubber, chlorinated butyl rubber, reactive chlorine type acrylic elastomer.
Among the present invention, the addition of thermal-reversible cross-linking agent is that per 100 parts of (quality) halogenated rubber rubbers add 1 to 25 part of linking agent.
The rubber unvulcanizate molding temperature is 170-180 ℃ among the present invention, and clamp time is 30-60min.
Testing method is as follows among the present invention.
The testing method of gel content in the cross-linked rubber sample: accurately take by weighing about cross-linked rubber sample 0.2g (being accurate to 0.0001g), place in the 100 order stainless (steel) wires,, in Soxhlet extractor, use refluxing toluene extracting 8h then in toluene, soaking 12h under the normal temperature.By residual gum sample Mass Calculation gel content in the stainless (steel) wire.Calculating formula:
G
2-dry back steel mesh and insoluble gel total mass, g;
G
1-steel mesh quality, g;
G
0-crosslinked sample mass, g.
Swelling capacity testing method: accurately take by weighing about cross-linked rubber sample 0.2g (being accurate to 0.001g), in toluene solvant, soak 24h.Calculate swelling capacity by glue sample gain in weight.Calculating formula:
W
1Quality after the-sample swelling, g;
W
0Quality before the-sample swelling, g.
Mechanic property test method: GB/T528-1998 tests according to GB, and the cross-linked rubber sample is cut into dumbbell III shape, sample thickness 2.0 ± 0.1mm, draw speed 200mm/min.The tensile property data comprise: tensile strength, elongation at break, stress at definite elongation, tension set etc.
Thermal reversibility can test and evaluation method: by the cross-linked rubber sample superimposed after once more heating and mould pressing moulding sample configuration of surface and add the thermoplastic processibility that thermal fluidity is judged the cross-linked rubber sample, and further investigate high temperature by the moment of torsion that the rotor vulkameter is measured the cross-linked rubber sample with variation of temperature and separate crosslinking feature.
Gel content, swelling capacity, tensile strength and rotor vulkameter torsion-testing result to the cross-linked rubber sample show, adopt two kinds of linking agents of the present invention all to realize the hot reversible crosslink of halogenated rubber.Crosslinked sample is carried out hot-forming, obtain that configuration of surface is smooth, successive reshaping film, and physical strength is good, show that the cross-linked rubber sample can carry out thermoplastic reprocessing.
The halogenated butyl rubber mixing formula is as follows among the present invention:
The mixing formula of table 1 halogenated butyl rubber
The composition quality umber
Halogenated butyl rubber 100
Calcinated argil 50-70
Talcum powder 7-10
Magnesium oxide 0.1-0.2
Titanium dioxide 3-5
White carbon black 0.13-0.50
Antioxidant 2246 1-2
Stearic acid 1-2
Linking agent 1-25
Description of drawings
Fig. 1 cross-linked rubber sample is implemented the mode of appearance after the heating and mould pressing reshaping.
The cross-linking curve (moment of torsion over time) that Fig. 2 rotor vulkameter is measured.
Fig. 3 rotor vulkameter is measured separates cross-linking curve (moment of torsion is with variation of temperature).
Embodiment
Embodiment 1
NaHCO with 100g deionized water, 0.83g sodium lauryl sulphate (SDS), 0.27g
3Join and be heated to dissolving fully in the reactor, add the pre-emulsification 20min of 5g Octyl acrylate (OA), get pre-emulsion.Temperature rises to and adds the aqueous solution 20mL that contains 0.05g Potassium Persulphate (KPS) after 75 ℃, after appearring in system, blue light drips aqueous solution 20mL that contains 0.15g KPS and the monomer miscellany of forming by 4-vinylpridine 10.51g, Octyl acrylate 9.74g and butyl acrylate 2.56g respectively, control monomer dropping time 3h, reaction 8h is continued in the intact back of monomer dropping, cooling discharging obtains milky emulsion.Emulsion solid content 20%, monomer conversion is about 90%.
It with the emulsion massfraction that obtains the polymkeric substance that obtains containing the pyridine side group behind 2% the NaCl solution breakdown of emulsion, this polymkeric substance pH is the NaOH aqueous solution soaking 24h of 9-10, dehydration back in 60 ℃ of drying under reduced pressure to constant weight, obtain linear amine-containing polymer linking agent (OA-4-VP linking agent), sealing is preserved standby.
Embodiment 2
With 500g deionized water, 5.36g sodium laurylsulfonate (SDS), 0.54gNaHCO
3Join in the reactor to dissolving fully, be warming up to 70 ℃ stable after, mixture (the vinylbenzene 99% that adds 6.00g vinylbenzene and Vinylstyrene (DVB), DVB1%) pre-emulsification 20min, pre-emulsion, add the aqueous solution 25mL prepolymerization contain 0.54g ammonium persulphate (APS), the mix monomer (vinylbenzene 99% of 34.00g vinylbenzene and Vinylstyrene appears dripping behind the blue light in the system for the treatment of, DVB1%), the dropping time is 4h.React 6h again after dripping the mix monomer of vinylbenzene and Vinylstyrene, drip the mix monomer (4-VP15%, vinylbenzene 85%) of 13.60g vinylbenzene and 4-vinylpridine then, continue reaction 16h, obtain having the translucent white emulsion of blue light.Emulsion solid content 10%, monomer conversion 96%.
Behind emulsion usefulness ethanol breakdown of emulsion, through high speed centrifugation, deionized water wash, collect pressed powder, in 50 ℃ of drying under reduced pressure, obtain having the Powdered amine-containing polymer linking agent (PS-N) of nucleocapsid structure.
Embodiment 3
The 27.78g sodium sand is added in the 442.52g anhydrous tetrahydro furan, under the condition of ice-water bath cooling and magnetic agitation, add cyclopentadiene (CPD) 59.57g gradually, reaction 24h.Gained cyclopentadiene sodium solution is mixed with excessive dry ice, and reaction 6h obtains dicyclopentadiene sodium diformate slurry, removes solvent and obtains dicyclopentadiene sodium diformate linking agent [DCPD (COONa) in 60 ℃ of drying under reduced pressure to constant weights through suction filtration then
2] 85.78g.
Embodiment 4
The dicyclopentadiene sodium diformate of getting the preparation of 20.20g embodiment 3 methods is dissolved in the 500mL deionized water, being neutralized to the pH value with 10% aqueous hydrochloric acid is 3, obtain dicyclopentadiene dioctyl phthalate slurry, the suction filtration dehydration, to constant weight, obtain 13.60g dicyclopentadiene dioctyl phthalate powder in 60 ℃ of drying under reduced pressure.Getting dicyclopentadiene dioctyl phthalate 11.25g is dissolved in the 103mL dehydrated alcohol, drip the ethanol solution 70mL that is dissolved with 7.00g potassium hydroxide then, neutralization reaction 22h, suction filtration remove solvent and in 60 ℃ of following drying under reduced pressure to constant weight, obtain dicyclopentadiene Potassium hydrogen diformate linking agent [DCPD (COOK)
2] 14.45g.
Embodiment 5
Get 100 parts of [mooney viscosity (ML of brominated butyl rubber
1+8, 125 ℃) 46, bromine content 2.1% (quality)], 8.4 parts of the amine-containing polymer linking agents (OA-4-VP) of embodiment 1,63 parts of calcinated argils (2000 order), 7 parts of talcum powder, 0.1 part in magnesium oxide, 3 parts of titanium dioxides, 0.13 part of white carbon black, 2 parts of antioxidant 2246s.Mixing 25min in mill, mixing even sheet down in 175 ℃ of following mold pressing 35min, is cooled to room temperature and obtains the cross-linked rubber sample behind the placement 24h.The moment of torsion of sample increases along with the prolongation of time in the mold process, and its cross-linking curve is seen accompanying drawing 2.With the cross-linked rubber sample cut into pieces, the 4 stacked backs of closing carry out compression molding in 185 ℃, obtain ganoid sample after being cooled to room temperature, its configuration of surface is seen accompanying drawing 1 (a).The performance test data of first cross-linked rubber sample and reshaping cross-linked rubber sample sees Table 2.
Table 2 is the performance data of linking agent cross-linked rubber sample with OA-4-VP
Embodiment 6
Get 100 parts of [mooney viscosity (ML of chlorinated butyl rubber
1+8, 125 ℃) 38 ± 5, cl content 1.2% (quality)], 25.0 parts of the Powdered amine-containing polymer linking agents (PS-N) of embodiment 2,60 parts of calcinated argils (2000 order), 10 parts of talcum powder, 0.1 part in magnesium oxide, 4 parts of titanium dioxides, 0.13 part of white carbon black, 1 part of antioxidant 2246,1 part of stearic acid.Mixing 25min in mill, mixing even sheet down in 175 ℃ of mold pressing 35min, is cooled to room temperature and obtains the cross-linked rubber sample behind the placement 24h.With the cross-linked rubber sample cut into pieces, the 4 stacked backs of closing carry out compression molding in 185 ℃, obtain ganoid sample after being cooled to room temperature, its mode of appearance is seen accompanying drawing 1 (b).The performance test data of first cross-linked rubber sample and reshaping cross-linked rubber sample sees Table 3.
Table 3 is a linking agent cross-linked rubber sample performance data with core-shell polymer PS-N
Embodiment 7
Get 100 parts of [mooney viscosity (ML of brominated butyl rubber
1+8, 125 ℃) 46, bromine content 2.1% (quality)], the dicyclopentadiene sodium diformate linking agent (DCPD (COONa) of embodiment 3
2) 3.8 parts, 50 parts of calcinated argils (2000 order), 7 parts of talcum powder, 0.2 part in magnesium oxide, 5 parts of titanium dioxides, 0.3 part of white carbon black, 1 part of antioxidant 2246.Mixing 25min in mill, mixing even down sheet is placed behind the 24h in 175 ℃ of following mold pressing 35min, obtains the cross-linked rubber sample after being cooled to room temperature.With the cross-linked rubber sample cut into pieces, the 4 stacked backs of closing carry out compression molding in 190 ℃, obtain ganoid sample after being cooled to room temperature, its mode of appearance is seen accompanying drawing 1 (c).The moment of torsion of crosslinked sample descends with the rising of temperature in the mold process, and it is separated cross-linking curve and sees accompanying drawing 3.The performance test data of first cross-linked rubber sample and reshaping cross-linked rubber sample sees Table 4.
Table 4 is with DCPD (COONa)
2Be linking agent cross-linked rubber sample performance data
Embodiment 8
Get 100 parts of [mooney viscosity (ML of brominated butyl rubber
1+8, 125 ℃) 46, bromine content 2.1% (quality)], the dicyclopentadiene Potassium hydrogen diformate linking agent (DCPD (COOK) of embodiment 4
2) 4.3 parts, 70 parts of calcinated argils (2000 order), 10 parts of talcum powder, 0.2 part in magnesium oxide, 4 parts of titanium dioxides, 0.2 part of white carbon black, 2 parts of antioxidant 2246s, 1 part of stearic acid.Mixing 25min in mill, mixing even down sheet is placed behind the 24h in 175 ℃ of following mold pressing 35min, obtains the cross-linked rubber sample after being cooled to room temperature.With the cross-linked rubber sample cut into pieces, 4 stacked close the back carry out compression molding in 190 ℃.The performance test data of first cross-linked rubber sample and reshaping cross-linked rubber sample sees Table 5.
Table 5 is with DCPD (COOK)
2Be linking agent cross-linked rubber sample performance data
Claims (10)
1. but a thermoplastic is reprocessed the preparation method of crosslinked halogenated butyl rubber, and it is characterized in that: linking agent is the polymkeric substance that contains the pyridine side group, and the crosslinking reaction of this linking agent is conciliate crosslinking reaction based on the reversible quaterisation of heat.
2. but a thermoplastic is reprocessed the preparation method of crosslinked halogenated butyl rubber, it is characterized in that: linking agent is the dicyclopentadiene diformate, the crosslinking reaction of this linking agent is based on esterification, and separates the contrary Diels-Alder cycloaddition reaction of crosslinking reaction based on the dicyclopentadiene bridged bond.
3. according to claim 1 and 2 described preparation methods, it is characterized in that: with linking agent, halogenated butyl rubber rubber, weighting agent and Synergist S-421 95 on the mixing roll mixing evenly after, in 150-190 ℃ of compression molding, make reversible crosslink rubber, preferred molding temperature is 160-180 ℃.Preferred rubber unvulcanizate prescription is (part): halogenated butyl rubber 100, calcinated argil 50-70, talcum powder 7-10, magnesium oxide 0.1-0.2, titanium dioxide 3-5, white carbon black 0.13-0.50, antioxidant 2246 1-2, stearic acid 1-2, linking agent 1-25.
4. reversible crosslink rubber according to claim 3 is characterized in that: the thermoplastic rework temperature of cross-linked rubber is 160-210 ℃, and preferred rework temperature is 175-195 ℃.
5. preparation method who contains pyridine side group polymkeric substance thermal-reversible cross-linking agent, it is characterized in that linking agent is prepared by radical polymerization by following component: the monomer, acrylate monomer, vinyl monomer, emulsifying agent, initiator, pH buffer reagent and the deionized water that contain the pyridine group.
6. according to claim 1 and 5 described preparation methods, it is characterized in that the employed monomer that contains the pyridine group comprises one or more in the following material: 2-chloro-4-allyl pyridine, 4-stibazole, 2-vinyl pyridine and 4-vinylpridine.
7. according to claim 1 and 5 described preparation methods, it is characterized in that employed non-pyridine monomer comprises the one or more combination in the following material: methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, butyl acrylate, butyl methacrylate, vinylformic acid isopentyl ester, Octyl acrylate, vinylbenzene, vinyl toluene.
8. according to claim 1 and the 5 described preparation methods that contain pyridine side group polymkeric substance, it is characterized in that, preferably make during polymerization by following compositions in weight percentage:
Contain pyridine group function monomer 5%～30%
Non-pyridine monomer 5%～60%
Initiator 0.5%～10.0%
Emulsifying agent 1.0%～10.0%
PH buffer reagent 0.5%～2.0%
The deionized water surplus
Said components weight percent sum is 100%;
9. the preparation method of dicyclopentadiene diformate according to claim 2 is characterized in that: make cyclopentadiene by the dicyclopentadiene thermo-cracking, make cyclopentadiene sodium by cyclopentadiene, obtain the dicyclopentadiene sodium diformate with carbon dioxide reaction again.
10. the preparation method of dicyclopentadiene diformate according to claim 2 is characterized in that: use in the protonic acid and the dicyclopentadiene sodium diformate, obtain the dicyclopentadiene dioctyl phthalate, prepare the dicyclopentadiene Potassium hydrogen diformate with neutralisation then.
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