CN102070745A - Fluorinated acrylate copolymer-containing resin and polymerization method thereof - Google Patents
Fluorinated acrylate copolymer-containing resin and polymerization method thereof Download PDFInfo
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- CN102070745A CN102070745A CN 200910199238 CN200910199238A CN102070745A CN 102070745 A CN102070745 A CN 102070745A CN 200910199238 CN200910199238 CN 200910199238 CN 200910199238 A CN200910199238 A CN 200910199238A CN 102070745 A CN102070745 A CN 102070745A
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Abstract
The invention provides a fluorinated acrylate copolymer-containing resin and a polymerization method thereof. The fluorinated acrylate copolymer-containing resin is a copolymer of (methyl) acrylic acid alkyl fluoride ester and methyl methacrylate. A preparation method comprises the following steps of: (1) feeding a mixed monomer, an initiator and a chain transfer agent into a polymerization kettle continuously, and then pressurizing and performing preliminary polymerization at the temperature of between 78 and 220 DEG C; (2) continuously feeding a product obtained in the step (1) into an exhaust screw extruder at the internal temperature of between 200 and 230 DEG C, performing high temperature polymerization, and extruding from the extruder to obtain the product or pelletizing to obtain the fluorinated acrylate copolymer-containing resin. The prepared product has high optical performance and adhesion, and can meet the application requirement of a low-loss plastic optical fiber.
Description
Technical field
The present invention relates to fluorinated acrylic ester-methacrylate co-polymer resin and manufacture method thereof.
Technical background
Along with the continuous development of plastic optical fiber in recent years, transparent low-refraction fluorine resin is developed with material as the plastic optical fiber cortex.Normally, this fluorine resin will satisfy following requirement: the first, and the refractive index that requires fluoro-resin is about 1.36～1.45, and its light transmittance requirement is more than 80%.The second, require the processing temperature of the processing temperature of fluoro-resin and core resin PMMA approaching, be about 200 degree, otherwise be difficult to obtain containing the plastic optical fiber of regular core skin structure.The 3rd, require fluoro-resin and PMMA resin to have adhesive property preferably, so the cortex resin of fluorine resin need have certain polar requirement.
At present, the fluoro-resin of the industrial production of China mainly is teflon resin, vinylidene etc., though these fluoro-resin satisfy the requirement of specific refractory power, resin crystallinity is all very high usually, is opaque resin substantially.In addition, the processing temperature of the above-mentioned fluoro-resin of mentioning is higher than the mold temperature (about 200 ℃) of PMMA resin far away generally all near 300 ℃.Plastic optical fiber differs too big with the processing temperature of core skin timber fat and the processing temperature of core PMMA resin, causes the core and the cortex machine-shaping difficulty of plastic optical fiber.In addition, the surface energy of the used fluoro-resin of industrial prior art is very low, and polarity is very little, and this makes that the cohesive force of these fluoro-resin and fiber-optic core material PMMA resin is not high, and there is defective in the fiber cores skin structure interface of making, thereby increases the transmission loss of optical fiber.
Summary of the invention
The objective of the invention is to disclose a kind of fluoro-acrylate copolymer resin and polymerization process thereof, to overcome the above-mentioned defective that prior art exists.
Fluoro-acrylate copolymer resin of the present invention is characterized in that, is that (methyl) vinylformic acid fluorinated alkyl esters is that first monomer and methyl methacrylate are the second monomeric multipolymer;
The general structure of described (methyl) vinylformic acid fluorinated alkyl esters is as follows:
Wherein: X is H or CH
3, R is the fluorinated alkyl of carbonatoms 3～10, F atomicity 4～12;
Weight-average molecular weight is 90,000～130,000, preferably 90,100～129,000;
Second-order transition temperature T
gBe higher than 82 ℃ and be lower than 100 ℃; Specific refractory power 1.36～1.43;
Preferably, (methyl) vinylformic acid fluorinated alkyl esters is selected from (methyl) vinylformic acid-2,2,3,3-tetrafluoro propyl ester, (methyl) vinylformic acid-2-trifluoromethyl-2,3,3,3-tetrafluoro propyl ester, (methyl) vinylformic acid-hexafluoro isopropyl ester, (methyl) vinylformic acid-2-trifluoromethyl-3,3,3-trifluoro propyl ester, (methyl) vinylformic acid-2,2,3,3,3-five fluorine propyl ester, (methyl) vinylformic acid-1,1,2,2-tetrahydrochysene perfluor ester in the last of the ten Heavenly stems, (methyl) vinylformic acid-1,1,2,2-tetrahydrochysene-1-methyl fluoride perfluor ester in the last of the ten Heavenly stems, (methyl) vinylformic acid-1,1-dimethyl-2,2,3,3-tetrafluoro propyl ester, (methyl) vinylformic acid-1,1-dimethyl-2,2,3,4,4,4-hexafluoro butyl ester, (methyl) vinylformic acid-1-ethyl-2,2,3,4,4,4-hexafluoro butyl ester, (methyl) vinylformic acid-octafluoro pentyl ester, (methyl) vinylformic acid-ten difluoro heptyl ester, (methyl) vinylformic acid-2,2,3,3-tetrafluoro propyl ester or (methyl) vinylformic acid-2,2,3,4,4, a kind of in the 4-hexafluoro butyl ester;
The preparation method of fluoro-acrylate copolymer resin of the present invention comprises the steps:
(1) mix monomer, initiator and the chain-transfer agent successive of described (methyl) vinylformic acid fluorinated alkyl esters and methyl methacrylate composition are sent into polymerization reaction kettle, the preliminary polymerization that under 78 ℃～220 ℃, pressurizes reaction;
Reaction pressure is 0.1～5.5MPa, and the residence time of preliminary polymerization is 3.5～12 hours;
(methyl) vinylformic acid fluorinated alkyl esters can adopt the method for bibliographical information be prepared (chemical research and application, the 16th the volume 5 phases, 671-672), perhaps adopt commercially available product;
The part by weight of (methyl) vinylformic acid fluorinated alkyl esters and methyl methacrylate is 60: 40～90: 10;
Described initiator is selected from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, benzoyl peroxide, tertbutyl peroxide, t-amyl peroxy hydrogen, dicumyl peroxide, isopropyl benzene hydroperoxide, ditertiary butyl peroxide, two t-amyl peroxy things, peroxidized t-butyl perbenzoate, the peroxidation trimethylacetic acid tert-butyl ester, peroxidation trimethylacetic acid tert-pentyl ester, 1,1-di-tert-butyl peroxide-3,3, the 5-trimethyl-cyclohexane, 2, the 2-azo-bis-iso-dimethyl, 1, the 1-cyclohexane di-tert-butyl peroxide, 2,5-dimethyl-2, the 5-di-t-butyl hexane peroxide, 4, a kind of in 4-two (tert-butyl hydroperoxide) n-butyl pentanoate or the methylethyl ketone peroxide, the initiator addition is 0.0001～0.02% of mixed monomer weight;
Described chain-transfer agent is selected from a kind of in the alkyl mercaptan that comprises 3～12 carbon atoms or the lauryl mercaptan; The addition of chain-transfer agent is 0.001～0.50% of mixed monomer weight;
The monomer conversion of preliminary polymerization reaction is controlled at 20～70%;
(2) with the product of step (1), it is 200 ℃～230 ℃ exhaust screw extrusion press that successive is sent into internal temperature, carries out the high temperature polymerization reaction, extrudes direct foreskin on core from forcing machine then;
Perhaps pass through pelletizing, obtain the fluorinated acrylic resin pellet that plastic optical fiber is used with the skin material.
The residence time of above-mentioned high temperature polymerization reaction is between 0.1～6 hour;
Monomeric transformation efficiency is more than 99.9%.
Term " monomer conversion " is defined as follows:
Monomeric transformation efficiency refers to: the weight that monomer carries out resultant copolymer resin after the polyreaction and monomer carry out the ratio of polyreaction mixed total monomer weight before.
Said reactor and exhaust screw rod are extruded and are the general equipment in this area, wherein, said exhaust screw extrusion press has venting port, and venting port is connected with the vacuum condensation system, to remove small-molecule substance remaining in the melt, the vacuum tightness of said vacuum system is 60～103kPa.
Mass polymerization agitator commonly used is installed in the said reactor; The unnecessary heat that the preliminary polymerization reaction discharges is removed by the interchanger that is arranged on reactor inside; Melt discharging connecting tube is installed in the bottom of reactor to be connected with the exhaust screw extrusion press.
Beneficial effect
The preparation method of the fluorinated acrylic resin that the present invention proposes is the pressurization continuous bulk polymerization.Bulk technique is not owing to add solvent, and therefore the product that makes has good optical property.In addition, utilize bulk technique, therefore the invention belongs to energy-saving technology also than the common energy of solution method technology saving more than 20%.The present invention utilizes the specific refractory power of transparent fluorinated acrylic resin of mass polymerization prepared about 1.37～1.42, processing temperature is low, be 170～200 degree, the similar of the core PMMA resin of the structure of fluorinated acrylic resin and optical fiber all contains ester group.Therefore fluorinated acrylic resin of the present invention and fiber-optic core material have good cohesive force.The fluoro-acrylate copolymer resin that adopts technical solution of the present invention to prepare can satisfy the application on the low-loss plastic optical fiber.
The fluorine-containing copolymer resin that the substance law continuous polymerization technique that proposes according to the present invention prepares has plurality of advantages, and the specific refractory power of the fluoroacrylic resin multipolymer that makes is about 1.36～1.43, and transmittance is more than 90%.The numerical aperture of the plastic optical fiber of preparation is below 0.35 millimeter, and the transmission loss when the excitation NA=0.1 of wavelength 650nm is below the 150dB/km.This fluorine-containing copolymer resin of preparation of the present invention can also satisfy the optics aspect to the strict demand that material proposes except can being used for preparing the cortex of plastic optical fiber, can be used in preparation high-grade optical goods or device.
Description of drawings
Fig. 1 is the infared spectrum of embodiment 1 gained fluorine-containing copolymer resin.
Fig. 2 is the infared spectrum of embodiment 2 gained fluorine-containing copolymer resins.
Fig. 3 is the infared spectrum of embodiment 3 gained fluorine-containing copolymer resins.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is further described.
(1) weight percent by trifluoroethyl methacrylate/methyl methacrylate/Diisopropyl azodicarboxylate/lauryl mercaptan is the mixed raw material of 70/30/0.00005/0.4;
(2) above-mentioned raw materials is transported in 30 liters the reactor with the flow velocity of 3kg per hour, reactor temperature is controlled at 130 ℃, and polymerization pressure is controlled at 1.5MPa, and the residence time of preliminary polymerization is 8.5 hours;
(3) the reactor material being delivered to degassing extruder continuously with Melt Pump handles.Forcing machine is 30 millimeters of internal diameters, and barrel length is 1.6 meters an exhaust screw extrusion press.The temperature of system forcing machine is at 200 ℃～230 ℃, and screw speed is that per minute 100 changes, and the unreacted monomer and the small-molecule substance that contain in the material are discharged from venting port.The vacuum degree control of first venting port of forcing machine is at 80kPa, and the vacuum tightness of second venting port is more than the 100kPa; The residence time of high temperature polymerization reaction is 48 minutes;
(4) the resin material of extruding from forcing machine pelletizing after air-cooled obtains the said fluoro-acrylate copolymer resin of the present invention;
The specific refractory power of gained fluorine-containing copolymer resin is 1.42, and weight-average molecular weight is 90100, and tensile strength is 60MPa (testing method ASTM D638), and modulus in flexure is 2500MPa (ASTMD638), and transmittance is 93%, second-order transition temperature T
gIt is 96 ℃.After being cortex and PMMA resin co-extrusion with this fluoro-resin, resulting plastic optical fiber fibre loss is 149dB/km.
The infrared spectrum of gained fluorine resin is seen shown in Figure 1.
Carry out with identical step according to embodiment 1 identical equipment, different is:
(1) to change the weight percent of methacrylic acid-ten difluoro heptyl ester/methyl methacrylate/dibenzoyl peroxide/lauryl mercaptan into be 70/30/0.00005/0.4 to raw material;
(2) raw material flow rate is 5kg per hour, and polymerization pressure is controlled at 2.0MPa, and the residence time of preliminary polymerization reaction is 5.1 hours;
(3) temperature of forcing machine is 200 ℃, and the residence time of high temperature polymerization reaction is 31 minutes;
Gained resin specific refractory power is 1.41, and weight-average molecular weight is 119000, and tensile strength is 64MPa (testing method ASTM D638), and transmittance is 93%, second-order transition temperature T
gIt is 85 ℃.
The infrared spectrogram of the fluorine resin for preparing as shown in Figure 2.Wherein, 2998cm
-1(undersaturated C-H stretching vibration), 1743cm
-1(C=O stretching vibration), 1300,1246 and 1171cm
-1(CF
3Stretching vibration), show that fluorine-containing ester group is arranged in the resin.
Carry out with identical step according to embodiment 1 identical reactor, different is:
(1) raw material changes into: methacrylic acid-2,2,3,4,4, the weight percent of 4-hexafluoro butyl ester/methyl methacrylate/Diisopropyl azodicarboxylate/lauryl mercaptan is 70/30/0.00005/0.4.
(2) raw material flow rate is 2.5kg per hour, and temperature is controlled at 200 ℃ in the reactor, and polymerization pressure is controlled at 3.5MPa, and the residence time of preliminary polymerization reaction is 10.2 hours;
(3) forcing machine changes 70 millimeters of internal diameters into, and barrel length is 3.2 meters, and screw speed is that per minute 90 changes, and the vacuum degree control of first venting port of forcing machine is at 70kPa, and the vacuum tightness of second venting port is 80kPa, and the vacuum tightness of the 3rd venting port is 103kPa; The temperature of forcing machine is 215 ℃, and the residence time of high temperature polymerization reaction is 350 minutes;
The resin specific refractory power for preparing is 1.40, and weight-average molecular weight is 118000, and tensile strength is 64MPa (testing method ASTM D638), and transmittance is 93%, second-order transition temperature T
gIt is 92 ℃.
The infared spectrum of the resin for preparing is seen shown in Figure 3.
Carry out with identical step according to embodiment 3 identical equipment, different is:
(1) raw material is: the weight percent of trifluoroethyl methacrylate/methyl methacrylate/methylethyl ketone peroxide/lauryl mercaptan is 70/30/0.00005/0.4;
(2) temperature of forcing machine is 210 ℃;
The resin specific refractory power for preparing is 1.42, and weight-average molecular weight is 129000, and tensile strength is 64MPa (testing method ASTM D638), and transmittance is 93%, second-order transition temperature T
gIt is 96 ℃.
The characteristic peak positions of the infared spectrum of the resin for preparing is with embodiment 1 infared spectrum.
Claims (10)
1. the fluoro-acrylate copolymer resin is characterized in that, is that (methyl) vinylformic acid fluorinated alkyl esters is that first monomer and methyl methacrylate are the second monomeric multipolymer;
The general structure of described (methyl) vinylformic acid fluorinated alkyl esters is as follows:
Wherein: X is H or CH
3, R is the fluorinated alkyl of carbonatoms 3～10, F atomicity 4～12.
2. fluoro-acrylate copolymer resin according to claim 1 is characterized in that, the second-order transition temperature T of multipolymer
gBe higher than 82 ℃ and be lower than 100 ℃; Specific refractory power 1.36～1.43.
3. fluoro-acrylate copolymer resin according to claim 1 is characterized in that, weight-average molecular weight is 90,000～130,000.
4. fluoro-acrylate copolymer resin according to claim 2 is characterized in that, weight-average molecular weight is 90,000～130,000.
5. according to each described fluoro-acrylate copolymer resin of claim 1～4, it is characterized in that (methyl) vinylformic acid fluorinated alkyl esters is selected from (methyl) vinylformic acid-2,2,3,3-tetrafluoro propyl ester, (methyl) vinylformic acid-2-trifluoromethyl-2,3,3,3-tetrafluoro propyl ester, (methyl) vinylformic acid-hexafluoro isopropyl ester, (methyl) vinylformic acid-2-trifluoromethyl-3,3,3-trifluoro propyl ester, (methyl) vinylformic acid-2,2,3,3,3-five fluorine propyl ester, (methyl) vinylformic acid-1,1,2,2-tetrahydrochysene perfluor ester in the last of the ten Heavenly stems, (methyl) vinylformic acid-1,1,2,2-tetrahydrochysene-1-methyl fluoride perfluor ester in the last of the ten Heavenly stems, (methyl) vinylformic acid-1,1-dimethyl-2,2,3,3-tetrafluoro propyl ester, (methyl) vinylformic acid-1,1-dimethyl-2,2,3,4,4,4-hexafluoro butyl ester, (methyl) vinylformic acid-1-ethyl-2,2,3,4,4,4-hexafluoro butyl ester, (methyl) vinylformic acid-octafluoro pentyl ester, (methyl) vinylformic acid-ten difluoro heptyl ester, (methyl) vinylformic acid-2,2,3,3-tetrafluoro propyl ester or (methyl) vinylformic acid-2,2,3,4,4, a kind of in the 4-hexafluoro butyl ester.
6. according to the preparation method of each described fluoro-acrylate copolymer resin of claim 1～5, comprise the steps:
(1) mix monomer that described (methyl) vinylformic acid fluorinated alkyl esters and methyl methacrylate are formed,, initiator and chain-transfer agent successive send into polymerization reaction kettle, the preliminary polymerization that pressurizes reaction under 78 ℃～220 ℃;
Reaction pressure is 0.1～5.5MPa;
(2) with the product of step (1), it is 200 ℃～230 ℃ exhaust screw extrusion press that successive is sent into internal temperature, carries out the high temperature polymerization reaction, extrudes from forcing machine then, obtains product;
Perhaps pass through pelletizing, obtain the fluoro-acrylate copolymer resin.
7. method according to claim 6 is characterized in that, first monomer and the second monomeric part by weight are 60: 40～90: 10.
8. method according to claim 6 is characterized in that, the residence time of preliminary polymerization is 3.5～12 hours, and the residence time of high temperature polymerization reaction is 0.1～6 hour.
9. method according to claim 6, it is characterized in that, described initiator is selected from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, benzoyl peroxide, tertbutyl peroxide, t-amyl peroxy hydrogen, dicumyl peroxide, isopropyl benzene hydroperoxide, ditertiary butyl peroxide, two t-amyl peroxy things, peroxidized t-butyl perbenzoate, the peroxidation trimethylacetic acid tert-butyl ester, peroxidation trimethylacetic acid tert-pentyl ester, 1,1-di-tert-butyl peroxide-3,3, the 5-trimethyl-cyclohexane, 2, the 2-azo-bis-iso-dimethyl, 1, the 1-cyclohexane di-tert-butyl peroxide, 2,5-dimethyl-2, the 5-di-t-butyl hexane peroxide, 4, a kind of in 4-two (tert-butyl hydroperoxide) n-butyl pentanoate or the methylethyl ketone peroxide, the initiator addition is 0.0001～0.02% of mixed monomer weight.
10. method according to claim 6 is characterized in that, described chain-transfer agent is selected from a kind of in the alkyl mercaptan that comprises 3～12 carbon atoms or the lauryl mercaptan; The addition of chain-transfer agent is 0.001～0.50% of mixed monomer weight.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103304725A (en) * | 2012-02-15 | 2013-09-18 | 罗门哈斯电子材料有限公司 | Self-assembled structures, method of manufacture thereof and articles comprising the same |
| CN108794679A (en) * | 2018-06-26 | 2018-11-13 | 重庆世纪之光科技实业有限公司 | A kind of plastic optical fiber core material and its preparation method and application |
| CN109810638A (en) * | 2019-01-25 | 2019-05-28 | 苏州凡赛特材料科技有限公司 | A kind of low-refraction optics pressure sensitive adhesive and its preparation method and application |
| CN111099688A (en) * | 2020-01-20 | 2020-05-05 | 成都辉聚光电材料有限公司 | Device and method for treating (methyl) acrylic acid wastewater |
| CN113355017A (en) * | 2021-05-06 | 2021-09-07 | 武汉长盈鑫科技有限公司 | Low-refractive-index optical fiber coating resin with high glass transition temperature |
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2009
- 2009-11-20 CN CN 200910199238 patent/CN102070745A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304725A (en) * | 2012-02-15 | 2013-09-18 | 罗门哈斯电子材料有限公司 | Self-assembled structures, method of manufacture thereof and articles comprising the same |
| CN103304725B (en) * | 2012-02-15 | 2016-08-24 | 罗门哈斯电子材料有限公司 | Self-assembled structures, its preparation method and include its goods |
| CN108794679A (en) * | 2018-06-26 | 2018-11-13 | 重庆世纪之光科技实业有限公司 | A kind of plastic optical fiber core material and its preparation method and application |
| CN108794679B (en) * | 2018-06-26 | 2020-12-22 | 重庆世纪之光科技实业有限公司 | Plastic optical fiber core layer material and preparation method and application thereof |
| CN109810638A (en) * | 2019-01-25 | 2019-05-28 | 苏州凡赛特材料科技有限公司 | A kind of low-refraction optics pressure sensitive adhesive and its preparation method and application |
| CN109810638B (en) * | 2019-01-25 | 2021-06-01 | 苏州凡赛特材料科技有限公司 | Low-refractive-index optical pressure-sensitive adhesive and preparation method and application thereof |
| CN111099688A (en) * | 2020-01-20 | 2020-05-05 | 成都辉聚光电材料有限公司 | Device and method for treating (methyl) acrylic acid wastewater |
| CN113355017A (en) * | 2021-05-06 | 2021-09-07 | 武汉长盈鑫科技有限公司 | Low-refractive-index optical fiber coating resin with high glass transition temperature |
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Application publication date: 20110525 |