CN102516469B - Grafted polypheylene ether resin and preparation method thereof - Google Patents
Grafted polypheylene ether resin and preparation method thereof Download PDFInfo
- Publication number
- CN102516469B CN102516469B CN 201110356374 CN201110356374A CN102516469B CN 102516469 B CN102516469 B CN 102516469B CN 201110356374 CN201110356374 CN 201110356374 CN 201110356374 A CN201110356374 A CN 201110356374A CN 102516469 B CN102516469 B CN 102516469B
- Authority
- CN
- China
- Prior art keywords
- polyphenylene oxide
- resin
- irradiation
- grafting
- oxide resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a grafted polyphenylene ether resin and a preparation method thereof, and belongs to the field of a polyphenylene ether resin. In the prior art, the chains of the polyphenylene ether molecules are easy to cross-link, the monomer is easily subjected to homopolymerization, and the mechanical property of the grafted polyphenylene ether resin is poor. The purpose of the present invention is to solve the problems in the prior art. The preparation method comprises: adopting beta rays or gamma rays to carry out pre-irradiation on the polyphenylene ether resin; mixing the pre-irradiated polyphenylene ether resin and the polyphenylene ether resin, and adding the resulting mixture to a reaction type double screw extruder; adding a graft monomer and an electron donor from a liquid feeding port of the reaction type double screw extruder to carry out reactive extrusion grafting to obtain the grafted polyphenylene ether resin. The water contact angle of the grafted polyphenylene ether resin prepared by the method is in the range of 50.6-82.6 DEG C, and the tensile strength of the grafted polyphenylene ether resin/polyamide 6 blending alloy can be 71.4 MPa.
Description
Technical field
The invention belongs to the polyphenylene oxide resin field, be specifically related to a kind of grafting polyphenylene oxide resin and preparation method thereof.
Background technology
Polyphenylene oxide is a kind of thermoplastic engineering plastic of high comprehensive performance, because of it has excellent resistant of high or low temperature, good mechanical performance, antifatigue, low suction, dimensional stability is good, higher creep-resistant property is arranged, the use temperature wide ranges, outstanding water-fast and anti-steam performance, advantage such as excellent flame-retardant performance and be widely used in fields such as electric, automobile, office apparatus.But because stress cracking takes place the polyphenylene oxide goods easily, and fluidity of molten is relatively poor, the forming process difficulty, and higher these of price all make the range of application of polyphenylene oxide be very restricted.
In order to overcome the above shortcoming of polyphenylene oxide, widen the Application Areas of polyphenylene oxide, at present the most frequently used method is that polyphenylene ether is carried out modification, main method of modifying be blend, glass strengthen, fill strengthen, toughness reinforcing etc.Because polyphenylene oxide is a kind of non-polar polymer, with some polar polymer blend be inconsistent, so need form the grafting polyphenylene oxide that contains polar group with grafted monomer and polyphenylene oxide resin copolymerization, could form compatible good blend alloy with other polar polymers.Grafting polyphenylene oxide mainly adopts solution grafting and the preparation of reaction extrusion molding at present.Solution grafting such as patent of invention " functionalized polyphenylene ether " (Granted publication CN1556830, the patent No. 02818360.6) are to adopt reactor to carry out grafting solution method, are the intermittent type operations, and will carry out loaded down with trivial details aftertreatment.The reaction extrusion molding normally adopts the small molecules organo-peroxide as initiator, as Chinese invention patent " a kind of polyphenylene oxide is the method for preparing compatilizer system by using of base material " (Granted publication CN101649032, the patent No. 200810063489.1) disclosed patented technology is described in, produce free radical with the copolyreaction between initiation grafting monomer and polyphenylene oxide resin by peroxide breakdown, yet because the decomposition rate of organo-peroxide is subjected to the influence of the chemical structure and the processing temperature of superoxide, the concentration and the life-span that produce free radical are difficult to control; And organo-peroxide and polyphenylene oxide resin consistency are poor, organo-peroxide can not be dispersed in the resin uniformly, cause the concentration distribution inequality of free radical in the system, therefore preparing the grafting polyphenylene oxide resin with organo-peroxide exists following shortcoming: homopolymerization, polyphenylene oxide resin molecular chain easily take place monomer, and easily generation is crosslinked, causes mechanical property or processing characteristics to become bad.
Summary of the invention
Polyphenylene oxide resin molecular chain of the prior art is easily crosslinked in order to solve, the problem of the polyphenylene oxide resin poor mechanical property after homopolymerization and the grafting easily takes place monomer, and a kind of grafting polyphenylene oxide resin and preparation method thereof is provided.
A kind of grafting polyphenylene oxide resin, as follows by the mass parts prescription:
The polyphenylene oxide resin of pre-irradiation, 65-85 part;
Polyphenylene oxide resin, 15-35 part;
The polyphenylene oxide resin of above-mentioned pre-irradiation and polyphenylene oxide resin are formed hybrid resin, and in 100 parts of the mass parts of hybrid resin, the mass parts of grafted monomer is 0.5-10 part, and giving the mass parts of electronics reagent is 0.05-2 part;
Described grafted monomer is acrylic or methacrylic acid;
Described is para benzoquinone or triphenylphosphate to electronics reagent.
The monomer of described polyphenylene oxide resin is 2,6-dimethyl-1,4-phenylate;
Described polyphenylene oxide resin limiting viscosity is 38-42ml/g.
A kind of preparation method of grafting polyphenylene oxide resin, its step and condition are:
(1) preparation of the polyphenylene oxide resin of pre-irradiation
Adopt rumbatron as irradiation source, under air atmosphere, carry out pre-irradiation with β ray polyphenylene ether resin, the pre-irradiation dosage range is 5kGy-40kGy; Or adopt
60Co under air atmosphere, carries out pre-irradiation with gamma-rays polyphenylene ether resin as irradiation source, and the pre-irradiation dosage range is 5kGy-40kGy, obtains the polyphenylene oxide resin of pre-irradiation;
(2) preparation of hybrid resin
By proportioning, the pre-irradiation polyphenylene oxide resin that step (1) is obtained joins in the high-speed mixer with polyphenylene oxide resin, mixes, and obtains hybrid resin; Wherein, described pre-irradiation polyphenylene oxide resin mass parts is 65-85 part, and the polyphenylene oxide resin mass parts is 15-35 part;
(3) the reaction extruding graft of hybrid resin and grafted monomer
The hybrid resin that step (2) is obtained joins in the response type twin screw extruder main hopper, with grafted monomer with inject for electronics reagent through response type twin screw extruder liquid charging opening, extrudes, check rod, cooling, granulation, obtains the grafting polyphenylene oxide resin; Wherein, hybrid resin is in 100 parts of mass parts, and the mass parts of described grafted monomer is 0.5-10 part, and described mass parts to electronics reagent is 0.05-2 part.
Described extrusion temperature is 200-290 ℃;
Described rotating speed is 75-150 rev/min.
Inventive principle: the preparation method of a kind of grafting polyphenylene oxide resin provided by the invention, adopt the pre-irradiation technology, under air atmosphere, the polyphenylene ether resin carries out pre-irradiation, the polyphenylene oxide resin of pre-irradiation produces the macromole superoxide on its molecular chain, the peroxide concentrations that produces is even, controlled, solved the crosslinked problem of polyphenylene oxide in reaction extruding graft process, with the macromole superoxide that on the polyphenylene oxide molecular chain, produces as initiator, to mix with polyphenylene oxide resin through the polyphenylene oxide of pre-irradiation, add in the response type twin screw extruder, grafted monomer and inject for electronics reagent through response type twin screw extruder liquid charging opening, through the reaction extruding graft, preparation grafting polyphenylene oxide resin.
Beneficial effect:
(1) the macromole peroxide concentrations that adopts the pre-irradiation method to produce is evenly distributed monomer homopolymerization and the polyphenylene oxide crosslinking reaction of having avoided the small molecules chemical initiator to cause;
(2) in mass percent, monomeric percentage of grafting is 0.1-4.5%, and grafting efficiency is 20-45%, has suppressed the crosslinking reaction of polyphenylene oxide resin in the grafting process for electronics reagent;
(3) with the grafting polyphenylene oxide resin of present method preparation since in the grafting polar group, its wetting ability increases, grafting polyphenylene oxide resin water contact angle is in 50.6 ° of-82.6 ° of scopes;
(4) grafting polyphenylene oxide resin and the polymeric amide with present method preparation has good consistency, and the tensile strength of grafting polyphenylether/polyamide 6 blend alloys can reach 71.4Mpa, improves a lot than the tensile strength of pure polyphenylether/polyamide 6 blend alloys.
Embodiment
Embodiment 1
(1) with limiting viscosity be the poly-2 of 38ml/g, 6-dimethyl-1, the 4-phenylate under air atmosphere, carries out pre-irradiation with the β ray on the rumbatron device, and pre-irradiation dosage is 10kGy, and what obtain pre-irradiation gathers 2,6-dimethyl-1,4-phenylate;
(2) pre-irradiation that step (1) is obtained is poly-2,6-dimethyl-1, and 85 parts of 4-phenylate resin quality parts and poly-2,6-dimethyl-1,4-phenylate resin quality part joins in the high-speed mixer for 15 parts together, mixes, and obtains hybrid resin;
(3) hybrid resin that step (2) is obtained joins in the Haake response type twin screw extruder main hopper, with mass parts is that 10 parts of vinylformic acid and mass parts are that 2 parts of para benzoquinone inject through the liquid charging opening of Haake response type twin screw extruder, react extruding graft, the screw diameter of described Haake response type twin screw extruder is 24mm, length-to-diameter ratio is 40, be followed successively by 200,230,250 from spout to each section of mouth mould temperature, 270,280,285,285,280 ℃, rotating speed is 100 rev/mins, and reactant is through extruding, check rod, cooling, granulation obtains the grafting polyphenylene oxide resin.
The percentage of grafting testing method is as follows:
In 250 milliliters of round-bottomed flasks, add 3.5 gram grafting polyphenylene oxide resins, add 120 milliliters of trichloromethanes again, heating for dissolving, after treating to dissolve fully, in acetone soln, precipitate through 60 order nickel screen filtered while hot, throw out is filtered, washs, and drying is 48 hours in 60 ℃ of vacuum drying ovens; Weighing an amount of dried deposit sample adding fills in the beaker of chloroform soln, after heating treats that sample dissolves fully, potassium hydroxide-ethanol solution with 0.0154 mol carries out titration, with mass percent is that 1% phenolphthalein ethanolic soln is as indicator, when titration to solution becomes redness and is terminal point when colour-fast in half a minute, the percentage of grafting mass percent calculates with following formula:
N is the concentration of potassium hydroxide-ethanol solution in the formula, unit: mol; V is for consuming the volume of potassium hydroxide-ethanol solution, unit: milliliter; M is the molar mass of grafted monomer, unit: gram/mole; W is for weighing dried deposit sample quality, unit: milligram.The grafting polyphenylene oxide resin that embodiment 1 is obtained is 4.5% with the percentage of grafting mass percent that above-mentioned percentage of grafting test way obtains.
Adopt sessile drop method, measure prepared grafting polyphenylene oxide thin slice and pure polyphenylene oxide slice surfaces water contact angle is respectively with DSA100 type shape liquid drop analysis instrument: 50.6 ° and 89.4 °.
With 50 parts of the grafting polyphenylene oxide resin mass parts that make, 50 parts of polyamide 6 resin quality parts join in the high-speed mixer together, mix, after the mixing, extrude through the reaction of SHJ-30 response type twin screw extruder, be followed successively by 200,220,245 from spout to each section of mouth mould temperature, 260,265,270,270,275,275,275,270 ℃, obtain grafting polyphenylether/polyamide 6 blend alloys.Make 50 parts of pure polyphenylene oxide mass parts by this technology, pure polyphenylether/polyamide 6 blend alloys that the polyamide 6 mass parts is 50 parts.The tensile strength of grafting polyphenylether/polyamide 6 blend alloys and pure polyphenylether/polyamide 6 blend alloys is respectively: 69.2MPa and 34.1MPa, and tension fracture deformation is respectively: 14.1% and 3.1%, establishing criteria GB/T1040.1-2006.
Embodiment 2
(1) with limiting viscosity be the poly-2 of 42ml/g, 6-dimethyl-1,4-phenylate resin under air atmosphere, carries out pre-irradiation with the β ray on the rumbatron device, and pre-irradiation dosage is 40kGy, and what obtain pre-irradiation gathers 2,6-dimethyl-1,4-phenylate;
(2) pre-irradiation that step (1) is obtained is poly-2,6-dimethyl-1, and 65 parts of 4-phenylate resin quality parts and poly-2,6-dimethyl-1,4-phenylate resin quality part joins in the high-speed mixer for 35 parts together, mixes, and obtains hybrid resin;
(3) hybrid resin that step (2) is obtained joins in the SHJ-30 response type twin screw extruder main hopper, be followed successively by 200 from spout to each section of mouth mould temperature, 220,240,260,270,280,280,285,285,290,280 ℃, 75 rev/mins of rotating speeds are that 0.5 part vinylformic acid and 0.05 portion of triphenylphosphate injects through the liquid charging opening of SHJ-30 response type twin screw extruder with mass parts, react extruding graft, reaction mass through extrude, traction, water-cooled, granulation, obtain the grafting polyphenylene oxide resin.
The percentage of grafting mass percent of the grafting polyphenylene oxide that the percentage of grafting test way among the employing embodiment 1 records is 0.2%.
Adopt sessile drop method, measure prepared grafting polyphenylene oxide thin slice and pure polyphenylene oxide slice surfaces water contact angle is respectively with DSA100 type shape liquid drop analysis instrument: 80.1 ° and 89.4 °.
With 70 parts of the grafting polyphenylene oxide resin mass parts that make, 30 parts of polyamide 6 resin quality parts join in the high-speed mixer together, mix, after the mixing, extrude through the reaction of SHJ-30 response type twin screw extruder, be followed successively by 200,220,245 from spout to each section of mouth mould temperature, 260,265,270,270,275,275,275,270 ℃, make grafting polyphenylether/polyamide 6 blend alloys.Make 70 parts of pure polyphenylene oxide mass parts by this technology, pure polyphenylether/polyamide 6 blend alloys that the polyamide 6 mass parts is 30 parts.The tensile strength of grafting polyphenylether/polyamide 6 blend alloys and pure polyphenylether/polyamide 6 blend alloys is respectively: 71.4MPa and 38.2MPa, tension fracture deformation is respectively: 15.2% and 3.4%.
Embodiment 3
(1) with limiting viscosity be the poly-poly-2 of 40ml/g, 6-dimethyl-1,4-phenylate resin under air atmosphere, carries out pre-irradiation with the β ray on the rumbatron device, and pre-irradiation dosage is 30kGy, and what obtain pre-irradiation gathers 2,6-dimethyl-1,4-phenylate;
(2) pre-irradiation that step (1) is obtained is poly-2,6-dimethyl-1, and 75 parts of 4-phenylate resin quality parts and poly-2,6-dimethyl-1,4-phenylate resin quality part joins in the high-speed mixer for 25 parts together, mixes, and obtains hybrid resin;
(3) hybrid resin that step (2) is obtained joins in the SHJ-30 response type twin screw extruder main hopper, be followed successively by 200 from spout to each section of mouth mould temperature, 230,250,270,270,280,285,285,285,290,280 ℃, 120 rev/mins of rotating speeds are that 5 parts of vinylformic acid and mass parts are that 1 part triphenylphosphate injects through the liquid charging opening of SHJ-30 response type twin screw extruder with mass parts, react extruding graft, reaction mass through extrude, traction, water-cooled, granulation, obtain the grafting polyphenylene oxide resin.
The percentage of grafting mass percent of the grafting polyphenylene oxide that the percentage of grafting test way among the employing embodiment 1 records is 1.5%.
Adopt sessile drop method, measure prepared grafting polyphenylene oxide thin slice and pure polyphenylene oxide slice surfaces water contact angle is respectively with DSA100 type shape liquid drop analysis instrument: 67.4 ° and 89.4 °.
With 60 parts of the grafting polyphenylene oxide resin mass parts that make, 40 parts of polyamide 6 resin quality parts join in the high-speed mixer together, mix, after the mixing, extrude through the reaction of SHJ-30 response type twin screw extruder, be followed successively by 200,220,245 from spout to each section of mouth mould temperature, 260,265,270,270,275,275,275,270 ℃, make grafting polyphenylether/polyamide 6 blend alloys.Make 60 parts of pure polyphenylene oxide mass parts by this technology, pure polyphenylether/polyamide 6 blend alloys that the polyamide 6 mass parts is 40 parts.The tensile strength of grafting polyphenylether/polyamide 6 blend alloys and pure polyphenylether/polyamide 6 blend alloys is respectively: 70.2MPa and 36.1MPa, tension fracture deformation is respectively: 10.1% and 3.3%.
Embodiment 4
(1) with limiting viscosity be the poly-2 of 40ml/g, 6-dimethyl-1,4-phenylate resin under air atmosphere, carries out pre-irradiation with the β ray on the rumbatron device, and pre-irradiation dosage is 5kGy, and what obtain pre-irradiation gathers 2,6-dimethyl-1,4-phenylate;
(2) pre-irradiation that step (1) is obtained is poly-2,6-dimethyl-1, and 80 parts of 4-phenylate resin quality parts and poly-2,6-dimethyl-1,4-phenylate resin quality part joins in the high-speed mixer for 20 parts together, mixes, and obtains hybrid resin;
(3) hybrid resin that step (2) is obtained joins in the SHJ-30 response type twin screw extruder main hopper, be followed successively by 200 from spout to each section of mouth mould temperature, 220,240,250,260,270,280,285,285,285,280 ℃, 110 rev/mins of rotating speeds are that 2 parts vinylformic acid and mass parts are that 0.05 part of para benzoquinone injects through the liquid charging opening of SHJ-30 response type twin screw extruder with mass parts, react extruding graft, reaction mass through extrude, traction, water-cooled, granulation, obtain the grafting polyphenylene oxide resin.
The percentage of grafting mass percent of the grafting polyphenylene oxide that the percentage of grafting test way among the employing embodiment 1 records is 0.7%.
Adopt sessile drop method, measure prepared grafting polyphenylene oxide thin slice and pure polyphenylene oxide slice surfaces water contact angle is respectively with DSA100 type shape liquid drop analysis instrument: 76.4 ° and 89.4 °.
With 50 parts of the grafting polyphenylene oxide resin mass parts that make, 50 parts of polyamide 6 resin quality parts join in the high-speed mixer together, mix, after the mixing, extrude, be followed successively by 200 to each section of mouth mould temperature from spout through the reaction of SHJ-30 response type twin screw extruder, 220,245,260,265,270,270,275,275,275,270 ℃, rotating speed makes grafting polyphenylether/polyamide 6 blend alloys.The tensile strength of pure polyphenylether/polyamide 6 blend alloys is respectively among grafting polyphenylether/polyamide 6 blend alloys and the embodiment 1: 66.1MPa and 34.1MPa, tension fracture deformation is respectively: 12.2% and 3.1%.
Embodiment 5
(1) with limiting viscosity be the poly-2 of 40ml/g, 6-dimethyl-1,4-phenylate resin under air atmosphere, carries out pre-irradiation with the β ray on the rumbatron device, and pre-irradiation dosage is 20kGy, and what obtain pre-irradiation gathers 2,6-dimethyl-1,4-phenylate;
(2) pre-irradiation that step (1) is obtained is poly-2,6-dimethyl-1, and 70 parts of 4-phenylate resin quality parts and poly-2,6-dimethyl-1,4-phenylate resin quality part joins in the high-speed mixer for 30 parts together, mixes, and obtains hybrid resin;
(3) hybrid resin that step (2) is obtained joins in the SHJ-30 response type twin screw extruder main hopper, be followed successively by 200 from spout to each section of mouth mould temperature, 210,230,250,270,280,280,285,285,285,280 ℃, 90 rev/mins of rotating speeds are that 8 parts of grafted monomer vinylformic acid and mass parts are 1.5 parts and inject for electronics reagent para benzoquinone through the liquid charging opening of SHJ-30 response type twin screw extruder with mass parts, react extruding graft, reaction mass through extrude, traction, water-cooled, granulation, obtain the grafting polyphenylene oxide resin.
The percentage of grafting mass percent of the grafting polyphenylene oxide that the percentage of grafting test way among the employing embodiment 1 records is 3.1%.
Adopt sessile drop method, measure prepared grafting polyphenylene oxide thin slice and pure polyphenylene oxide slice surfaces water contact angle is respectively with DSA100 type shape liquid drop analysis instrument: 56.2 ° and 89.4 °.
With 40 parts of the grafting polyphenylene oxide resin mass parts that make, 60 parts of polyamide 6 resin quality parts join in the high-speed mixer together, mix, after the mixing, extrude through the reaction of SHJ-30 response type twin screw extruder, be followed successively by 200,220,245 from spout to each section of mouth mould temperature, 260,265,270,270,275,275,275,270 ℃, make grafting polyphenylether/polyamide 6 blend alloys.Make 40 parts of pure polyphenylene oxide mass parts by this technology, pure polyphenylether/polyamide 6 blend alloys that the polyamide 6 mass parts is 60 parts.The tensile strength of grafting polyphenylether/polyamide 6 blend alloys and pure polyphenylether/polyamide 6 blend alloys is respectively: 54.6MPa and 31.8MPa, tension fracture deformation is respectively: 3.1% and 2.9%.
Embodiment 6
(1) with limiting viscosity be the poly-2 of 40ml/g, 6-dimethyl-1,4-phenylate resin, under air atmosphere,
60Carry out pre-irradiation with gamma-rays on the Co device, pre-irradiation dosage is 5kGy, and what obtain pre-irradiation gathers 2,6-dimethyl-1,4-phenylate;
(2) pre-irradiation that step (1) is obtained is poly-2,6-dimethyl-1, and 85 parts of 4-phenylate resin quality parts and poly-2,6-dimethyl-1,4-phenylate resin quality part joins in the high-speed mixer for 15 parts together, mixes, and obtains hybrid resin;
(3) hybrid resin that step (2) is obtained joins in the SHJ-30 response type twin screw extruder main hopper, be followed successively by 200 from spout to each section of mouth mould temperature, 210,230,250,270,280,285,285,285,285,280 ℃, 120 rev/mins of rotating speeds are that 3 parts of grafted monomer methacrylic acids and mass parts are 2 parts injecting to the liquid charging opening of electronics phosphorylating reagent triphenylmethyl methacrylate through SHJ-30 response type twin screw extruder with mass parts, react extruding graft, reaction mass through extrude, traction, water-cooled, granulation, obtain the grafting polyphenylene oxide resin.
The percentage of grafting mass percent of the grafting polyphenylene oxide that the percentage of grafting test way among the employing embodiment 1 records is 0.8%.
Adopt sessile drop method, measure prepared grafting polyphenylene oxide thin slice and pure polyphenylene oxide slice surfaces water contact angle is respectively with DSA100 type shape liquid drop analysis instrument: 74.8 ° and 89.4 °.
With 30 parts of the grafting polyphenylene oxide resin mass parts that make, 70 parts of polyamide 6 resin quality parts join in the high-speed mixer together, mix, after the mixing, extrude through the reaction of SHJ-30 response type twin screw extruder, be followed successively by 200,220,245 from spout to each section of mouth mould temperature, 260,265,270,270,275,275,275,270 ℃, make grafting polyphenylether/polyamide 6 blend alloys.Make 30 parts of pure polyphenylene oxide mass parts by this technology, pure polyphenylether/polyamide 6 blend alloys that the polyamide 6 mass parts is 70 parts.The tensile strength of grafting polyphenylether/polyamide 6 blend alloys and pure polyphenylether/polyamide 6 blend alloys is respectively: 41.6MPa and 29.2MPa, tension fracture deformation is respectively: 3.0% and 2.7%.
Embodiment 7
(1) with limiting viscosity be the poly-2 of 40ml/g, 6-dimethyl-1,4-phenylate resin, under air atmosphere,
60Carry out pre-irradiation with gamma-rays on the Co device, pre-irradiation dosage is 40kGy, and what obtain pre-irradiation gathers 2,6-dimethyl-1,4-phenylate;
(2) pre-irradiation that step (1) is obtained is poly-2,6-dimethyl-1, and 80 parts of 4-phenylate resin quality parts and poly-2,6-dimethyl-1,4-phenylate resin quality part joins in the high-speed mixer for 20 parts together, mixes, and obtains hybrid resin;
(3) hybrid resin that step (2) is obtained joins in the SHJ-30 response type twin screw extruder main hopper, be followed successively by 200 from spout to each section of mouth mould temperature, 210,230,250,270,285,285,290,290,285,280 ℃, 140 rev/mins of rotating speeds are that 7 parts of grafted monomer methacrylic acids and mass parts are 0.8 part and inject for electronics reagent para benzoquinone through the liquid charging opening of SHJ-30 response type twin screw extruder with mass parts, react extruding graft, reaction mass through extrude, traction, water-cooled, granulation, obtain the grafting polyphenylene oxide resin.
The percentage of grafting mass percent of the grafting polyphenylene oxide that the percentage of grafting test way among the employing embodiment 1 records is 1.7%.
Adopt sessile drop method, measure prepared grafting polyphenylene oxide thin slice and pure polyphenylene oxide slice surfaces water contact angle is respectively with DSA100 type shape liquid drop analysis instrument: 66.7 ° and 89.4 °.
With 50 parts of the grafting polyphenylene oxide resin mass parts that make, 50 parts of polyamide 6 resin quality parts join in the high-speed mixer together, mix, after the mixing, extrude through the reaction of SHJ-30 response type twin screw extruder, be followed successively by 200,220,245 from spout to each section of mouth mould temperature, 260,265,270,270,275,275,275,270 ℃, make grafting polyphenylether/polyamide 6 blend alloys.The tensile strength of pure polyphenylether/polyamide 6 blend alloys is respectively among grafting polyphenylether/polyamide 6 blend alloys and the embodiment 1: 67.2MPa and 34.1MPa, tension fracture deformation is respectively: 13.1% and 3.1%.
Embodiment 8
(1) with limiting viscosity be the poly-2 of 40ml/g, 6-dimethyl-1,4-phenylate resin, under air atmosphere,
60Carry out pre-irradiation with gamma-rays on the Co device, pre-irradiation dosage is 25kGy, and what obtain pre-irradiation gathers 2,6-dimethyl-1,4-phenylate;
(2) pre-irradiation that step (1) is obtained is poly-2,6-dimethyl-1, and 85 parts of 4-phenylate resin quality parts and poly-2,6-dimethyl-1,4-phenylate resin quality part joins in the high-speed mixer for 15 parts together, mixes, and obtains hybrid resin;
(3) hybrid resin that step (2) is obtained joins in the SHJ-30 response type twin screw extruder main hopper, be followed successively by 200 from spout to each section of mouth mould temperature, 210,230,250,270,280,280,290,290,285,280 ℃, 80 rev/mins of rotating speeds, with mass parts is that 10 parts of grafted monomer methacrylic acids and mass parts are 0.6 part and inject for electronics phosphorylating reagent triphenylmethyl methacrylate through the liquid charging opening of SHJ-30 response type twin screw extruder, react the extruding graft reaction mass through extrude, traction, water-cooled, granulation, obtain the grafting polyphenylene oxide resin.
The percentage of grafting mass percent of the grafting polyphenylene oxide that the percentage of grafting test way among the employing embodiment 1 records is 2.3%.
Adopt sessile drop method, measure prepared grafting polyphenylene oxide thin slice and pure polyphenylene oxide slice surfaces water contact angle is respectively with DSA100 type shape liquid drop analysis instrument: 62.3 ° and 89.4 °.
With 50 parts of the grafting polyphenylene oxide resin mass parts that make, 50 parts of polyamide 6 resin quality parts join in the high-speed mixer together, mix, after the mixing, extrude through the reaction of SHJ-30 response type twin screw extruder, be followed successively by 200,220,245 from spout to each section of mouth mould temperature, 260,265,270,270,275,275,275,270 ℃, make grafting polyphenylether/polyamide 6 blend alloys.The tensile strength of pure polyphenylether/polyamide 6 blend alloys is respectively among grafting polyphenylether/polyamide 6 blend alloys and the embodiment 1: 68.9MPa and 34.1MPa, tension fracture deformation is respectively: 14.4% and 3.1%.
Embodiment 9
(1) with limiting viscosity be the poly-2 of 40ml/g, 6-dimethyl-1,4-phenylate resin, under air atmosphere,
60Carry out pre-irradiation with gamma-rays on the Co device, pre-irradiation dosage is 15kGy, and what obtain pre-irradiation gathers 2,6-dimethyl-1,4-phenylate;
(2) pre-irradiation that step (1) is obtained is poly-2,6-dimethyl-1, and 80 parts of 4-phenylate resin quality parts and poly-2,6-dimethyl-1,4-phenylate resin quality part joins in the high-speed mixer for 20 parts together, mixes, and obtains hybrid resin;
(3) hybrid resin that step (2) is obtained joins in the SHJ-30 response type twin screw extruder main hopper, be followed successively by 200 from spout to each section of mouth mould temperature, 210,230,250,270,280,280,285,285,285,280 ℃, 150 rev/mins of rotating speeds are that 0.5 part of grafted monomer methacrylic acid and mass parts are 0.2 part and inject for electronics reagent para benzoquinone through the liquid charging opening of SHJ-30 response type twin screw extruder with mass parts, react extruding graft, reaction mass through extrude, traction, water-cooled, granulation, obtain the grafting polyphenylene oxide resin.
The percentage of grafting mass percent of the grafting polyphenylene oxide that the percentage of grafting test way among the employing embodiment 1 records is 0.1%.
Adopt sessile drop method, measure prepared grafting polyphenylene oxide thin slice and pure polyphenylene oxide slice surfaces water contact angle is respectively with DSA100 type shape liquid drop analysis instrument: 82.6 ° and 89.4 °.
With 50 parts of the grafting polyphenylene oxide resin mass parts that make, 50 parts of polyamide 6 resin quality parts join in the high-speed mixer together, mix, after the mixing, extrude through the reaction of SHJ-30 response type twin screw extruder, be followed successively by 200,220,245 from spout to each section of mouth mould temperature, 260,265,270,270,275,275,275,270 ℃, make grafting polyphenylether/polyamide 6 blend alloys.The tensile strength of pure polyphenylether/polyamide 6 blend alloys is respectively among grafting polyphenylether/polyamide 6 blend alloys and the embodiment 1: 64.9MPa and 34.1MPa, tension fracture deformation is respectively: 4.1% and 3.1%.
Claims (6)
1. a grafting polyphenylene oxide resin is characterized in that, and is as follows by the mass parts prescription:
The polyphenylene oxide resin of pre-irradiation, 65-85 part;
Polyphenylene oxide resin, 15-35 part;
The polyphenylene oxide resin of above-mentioned pre-irradiation and polyphenylene oxide resin are formed hybrid resin, and in 100 parts of the mass parts of hybrid resin, the mass parts of grafted monomer is 0.5-10 part, and giving the mass parts of electronics reagent is 0.05-2 part;
Described grafted monomer is acrylic or methacrylic acid;
Described is para benzoquinone or triphenylphosphate to electronics reagent;
The preparation method of the polyphenylene oxide resin of described pre-irradiation is: adopt rumbatron as irradiation source, under air atmosphere, carry out pre-irradiation with β ray polyphenylene ether resin, the pre-irradiation dosage range is 5kGy-40kGy; Or adopt
60Co under air atmosphere, carries out pre-irradiation with gamma-rays polyphenylene ether resin as irradiation source, and the pre-irradiation dosage range is 5kGy-40kGy, obtains the polyphenylene oxide resin of pre-irradiation.
2. a kind of grafting polyphenylene oxide resin as claimed in claim 1 is characterized in that the monomer of described polyphenylene oxide resin is 2,6-dimethyl-1,4-phenylate.
3. a kind of grafting polyphenylene oxide resin as claimed in claim 1 is characterized in that described polyphenylene oxide resin limiting viscosity is 38-42mL/g.
4. the preparation method of a kind of grafting polyphenylene oxide resin according to claim 1 is characterized in that, its step and condition are as follows:
(1) preparation of the polyphenylene oxide resin of pre-irradiation
Adopt rumbatron as irradiation source, under air atmosphere, carry out pre-irradiation with β ray polyphenylene ether resin, the pre-irradiation dosage range is 5kGy-40kGy; Or adopt
60Co under air atmosphere, carries out pre-irradiation with gamma-rays polyphenylene ether resin as irradiation source, and the pre-irradiation dosage range is 5kGy-40kGy, obtains the polyphenylene oxide resin of pre-irradiation;
(2) preparation of hybrid resin
By proportioning, the pre-irradiation polyphenylene oxide resin that step (1) is obtained joins in the high-speed mixer with polyphenylene oxide resin, mixes, and obtains hybrid resin; Wherein, described pre-irradiation polyphenylene oxide resin mass parts is 65-85 part, and the polyphenylene oxide resin mass parts is 15-35 part;
(3) the reaction extruding graft of hybrid resin and grafted monomer
The hybrid resin that step (2) is obtained joins in the response type twin screw extruder main hopper, with grafted monomer with inject for electronics reagent through response type twin screw extruder liquid charging opening, extrudes, check rod, cooling, granulation, obtains the grafting polyphenylene oxide resin; Wherein, hybrid resin is in 100 parts of mass parts, and the mass parts of described grafted monomer is 0.5-10 part, and described mass parts to electronics reagent is 0.05-2 part.
5. the preparation method of a kind of grafting polyphenylene oxide resin as claimed in claim 4 is characterized in that, the extrusion temperature in the described step (3) is 200-290 ° of C.
6. the preparation method of a kind of grafting polyphenylene oxide resin as claimed in claim 4 is characterized in that, described step (3) medium speed is 75-150 rev/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110356374 CN102516469B (en) | 2011-11-11 | 2011-11-11 | Grafted polypheylene ether resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110356374 CN102516469B (en) | 2011-11-11 | 2011-11-11 | Grafted polypheylene ether resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102516469A CN102516469A (en) | 2012-06-27 |
| CN102516469B true CN102516469B (en) | 2013-07-24 |
Family
ID=46287572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110356374 Active CN102516469B (en) | 2011-11-11 | 2011-11-11 | Grafted polypheylene ether resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102516469B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI629295B (en) * | 2016-09-23 | 2018-07-11 | 台光電子材料股份有限公司 | Phosphorus-containing ethylene polyphenylene ether, resin composition containing phosphorus-containing ethylene polyphenylene ether, and products thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1687168A (en) * | 2005-04-04 | 2005-10-26 | 中国科学院广州化学研究所 | Method for preparing grouting material of modified polyacrylamide |
| CN101245181A (en) * | 2008-03-25 | 2008-08-20 | 广州市合诚化学有限公司 | High-performance environment protection type flame-proof polyphenylene oxide composite material and manufacture method thereof |
-
2011
- 2011-11-11 CN CN 201110356374 patent/CN102516469B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1687168A (en) * | 2005-04-04 | 2005-10-26 | 中国科学院广州化学研究所 | Method for preparing grouting material of modified polyacrylamide |
| CN101245181A (en) * | 2008-03-25 | 2008-08-20 | 广州市合诚化学有限公司 | High-performance environment protection type flame-proof polyphenylene oxide composite material and manufacture method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102516469A (en) | 2012-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102030960B (en) | Preparation method of high-melt-strength polyolefine comprising hybrid long branch-chain structure | |
| CN101125947A (en) | High fused mass strength polypropylene containing long branched chain structure and preparing method thereof | |
| CN103146105A (en) | Reaction extrusion polymerization method of functional acrylate resin | |
| CN105418835A (en) | Preparing method for core-shell structure functionality acrylate polymer particles for toughening polycarbonate | |
| CN102443109B (en) | Functionalized ultrahigh-molecular-weight polyethylene resin and preparation method thereof | |
| CN101812161B (en) | Polyethylene bonding resin and preparation method thereof | |
| CN102516469B (en) | Grafted polypheylene ether resin and preparation method thereof | |
| CN110452469A (en) | A kind of modified polypropylene material and preparation method thereof | |
| CN106928540A (en) | A kind of just heat-resistance polypropylene/polyphenylene sulfide PP/PPS alloys and preparation method thereof high | |
| CN109679243A (en) | A kind of heat-and corrosion-resistant polyvinyl chloride supplying drainage and preparation method thereof | |
| CN109627539A (en) | Polyethylene composition and preparation method thereof with excellent resistance to cracking energy | |
| CN100448902C (en) | Acrylic resin with high bath strength, and preparation method | |
| CN102775620B (en) | Preparation method for organic-inorganic hybrid polyolefin elastomer irradiation cross-linking system | |
| CN111234471A (en) | PBT composite material with low linear thermal expansion coefficient and preparation method thereof | |
| CN103435747B (en) | A kind of polyacrylonitrile copolymer spinning solution and preparation method thereof | |
| CN111040282A (en) | High-strength high-heat-resistance polyethylene glass fiber reinforced belt and preparation method thereof | |
| CN1986589B (en) | Polypropylene resin with high melt strength and its preparing method | |
| CN110003598B (en) | High-fluidity nylon 11, product thereof and preparation method thereof | |
| CN109206738A (en) | A kind of high-intensitive, high tenacity fibre reinforced polypropylene injection molding material | |
| CN116144187B (en) | Polylactic acid composite material and preparation method and application thereof | |
| CN115368686B (en) | Glass fiber reinforced polystyrene material and preparation method and application thereof | |
| CN114907526B (en) | Preparation method of high-performance maleic anhydride grafted POE | |
| CN114656598A (en) | Nylon toughening agent and preparation method thereof | |
| CN109320898B (en) | Nano montmorillonite modified PA6/ABS alloy and preparation method thereof | |
| CN104559205B (en) | A kind of preparation method of in-situ flexible polypropylene alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |