JP2003268039A - Method for producing fluorine-containing polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a fluorine-containing polymer which has excellent coloring stability under a high-temperature and high- humidity condition even though the polymer is not subjected to stabilizing treatment, such as fluorinating treatment. <P>SOLUTION: This method for producing the fluorine-containing polymer comprises using a fluorine-containing dialkyl peroxide as a polymerization initiator to conduct bulk polymerization of a fluorine-containing monomer having a fluorine-containing ring structure or another fluorine-containing monomer having two or more polymerizable double bonds, so that the fluorine-containing polymer of which the main chain has fluorine-containing aliphatic ring structures is obtained. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to fluorination treatment and the like.
High transparency and high temperature and humidity without stabilization
The present invention relates to a method for producing a fluorine-containing polymer having excellent color resistance. [0002] Conventionally, high thermal stability and chemical stability
Excellent in properties and has a fluorine-containing aliphatic ring structure in the main chain
As a method for producing a silicon polymer, for example, JP-A-20
The method disclosed in Japanese Patent No. 00-1511 is known.
The That is, in the publication, [C₆F₅C (O)
O]₂, [C₆F₅C (CH₃)₂C (O) O]₂Etc.
Fluorine-containing diacyl peroxide is used as a polymerization initiator
I have been able to. [0003] However, as described in the above publication
Among the above conditions, fluorine-containing diacyl peroxide having an aromatic ring
The fluorine-containing polymer was prepared using xoxide as a polymerization initiator.
When it is manufactured, the stabilization treatment such as fluorination treatment
If this is not the case, it will become colored when stored for a long time under high temperature and high humidity.
I found out that there was a problem. The cause of this coloring
It is presumed to be due to a colored substance derived from the polymerization initiator. Special
A compound having an aromatic ring with a fluorine atom bonded thereto is polymerized.
When used as an initiator, this aromatic ring is oxidized and becomes quinone type
Resulting in the formation of a colored compound
it is conceivable that. Accordingly, the present invention solves the above-mentioned problems and provides a
High transparency without stabilizing treatment such as nitrogen treatment
Fluoropolymer with excellent color resistance under high temperature and high humidity
A method of manufacturing is provided. [0005] The present invention provides a fluorinated dia.
Using a ruperoxide polymerization initiator,
Bulk polymerization of monomer (a), (b), (c) or (d)
And fluorine-containing polymerization having a fluorine-containing aliphatic ring structure in the main chain
A process for producing a fluoropolymer characterized in that
provide. (A) A fluorine-containing monomer having a fluorine-containing ring structure. (B) Fluorine-containing monomer having two or more polymerizable double bonds
body. (C) Fluorinated monomer (a) and fluorinated monomer
(B). (D) One type selected from fluorine-containing monomers (a) and (b)
The above fluorine-containing monomer, fluorine-containing monomer (a),
Other fluorine-containing monomers other than (b). [0006] DETAILED DESCRIPTION OF THE INVENTION Polymerization initiator used in the present invention.
Is a fluorine-containing dialkyl peroxide compound (hereinafter referred to as excess
This is referred to as oxide Z. ). That is, the corresponding foot
It is a form of peroxide of silicon alkyl ether. The peracid
Compound Z does not have an aromatic ring. The peroxide Z is
Does not have a carbonyl group. Aromatic ring or carbonyl
If it has a group, it is possible to form a colored substance under high temperature and high humidity.
There is a potential. The alkyl chain of the peroxide Z is linear.
May be branched, but branching is the stability of peroxide Z
And more preferable. The alkyl chain is symmetrical or asymmetrical
However, the symmetry is that the peroxide Z is easy to manufacture.
preferable. The alkyl chain preferably has 3 to 10 carbon atoms.
3 to 8 are more preferable. The peroxide Z is substantially
It preferably contains no hydrogen atoms and is a perfluorinated compound.
More preferably, it is a product. Perfluoro compound
The phase between the peroxide Z and the fluorine-containing monomer described later
Improvement in solubility, thermal stability of the resulting fluoropolymer
Is preferable from the viewpoint of improvement. As a specific example of peroxide Z
Is perfluoro (di-tert-butylperoxy
), Perfluoro (di-tert-pentylperoxy)
Sid). The synthesis of the peroxide Z is described by D.E. Gould et a
l., J.Chem.Soc., Chem.Commun., (216) 1970
The law can be adopted. For example, perfluoro (di-tert-
Butyl peroxide) is perfluoro-tert-butyl
Luoalcohol with ClF₃It is obtained by acting. Ratio of peroxide Z to fluorine-containing monomer
Is 0.01 to 100 parts by mass with respect to 100 parts by mass of the fluorinated monomer.
5 parts by mass is preferable, and 0.1 to 1 part by mass is more preferable.
Yes. When the proportion of peroxide Z was too low, it was obtained
A large amount of unreacted fluorine-containing monomer remains in the fluorine-containing polymer.
Deteriorating physical properties of fluoropolymers, coloring at high temperatures, etc.
This is not preferable. Also, the percentage of peroxide Z is too high
The proportion of peroxide Z that did not contribute to the polymerization is
Increasing due to the induced decomposition of the excess peroxide Z
Preferred because the fluoropolymer becomes cloudy or colored
Absent. Reaction of bulk polymerization using these peroxides Z
The reaction temperature is preferably 30 to 150 ° C., and 40 to 120 ° C.
More preferred. In the present invention, the obtained fluorine-containing polymerization
The body is stable without any fluorination treatment
Excellent in properties. However, the fluorine-containing material obtained by bulk polymerization
Fluorine polymer is thermally stable by treating with fluorine gas
Can be further enhanced. For example, fluoropolymer
Temperature below the glass transition temperature or temperature below the softening temperature
Or turbidity or coloring by exposure to fluorine gas
Can be suppressed. The action of fluorine gas is not always clear
However, fluorine gas is attached to the double bond of unreacted monomer.
In addition, the unreacted monomer has changed to a stable saturated compound
It seems to be. As a result, the thermal stability of the fluoropolymer
It seems to improve the performance. Also, if necessary
Volatile substances are removed by heating and vacuum drying the fluorine polymer.
Removal can also suppress the occurrence of cloudiness or coloring
It is effective in. Fluoropolymer obtained in the present invention
As for fluorine content 40-75 mass%,
A fluorine-containing polymer having a number average molecular weight of 10,000 to 1,000,000 is
preferable. The fluorine content is more preferably 50-70% by mass
The number average molecular weight is more preferably 20,000 to 500,000. In the present invention, the fluorine-containing material used for bulk polymerization.
The fluorine monomer includes the following fluorine-containing monomers (a), (b),
(C) or (d). (A) A fluorine-containing monomer having a fluorine-containing ring structure. (B) Fluorine-containing monomer having two or more polymerizable double bonds
body. (C) Fluorinated monomer (a) and fluorinated monomer
(B). (D) One type selected from fluorine-containing monomers (a) and (b)
The above fluorine-containing monomer, fluorine-containing monomer (a),
Other fluorine-containing monomers other than (b). As the fluorine-containing monomer (a), perful
Oro (2,2-dimethyl-1,3-dioxole) etc.
Can be mentioned. As the fluorine-containing monomer (b), perful
Oro (allyl vinyl ether), perfluoro (buteni
Fluorine-containing monomer that can be cyclopolymerized
Is mentioned. Other than fluorine-containing monomers (a) and (b)
Examples of fluorine-containing monomers include tetrafluoroethylene and black
Rotrifluoroethylene, perfluoro (methyl vinyl)
Does not have a fluorine-containing ring structure such as ether) and can be cyclopolymerized
Non-fluorinated monomers. Preferred fluorine-containing unit
The monomer (or combination of fluorine-containing monomers)
These are the elementary monomers (a), (b) and (c). Obtained by polymerizing fluorine-containing monomer (a)
Fluorine-containing polymer, fluorine-containing monomer (a), and fluorine-containing polymer
Polymerizes other fluorine-containing monomers other than monomers (a) and (b)
The fluorine-containing polymer obtained in this way is JP-B 63-1896.
4 etc. Further, fluorine-containing monomer (b)
Fluoropolymers obtained by cyclopolymerization of
Other than monomer (b) and fluorine-containing monomer (a), (b)
Fluoropolymer obtained by polymerizing the above fluorinated monomer
Are disclosed in Japanese Patent Laid-Open Nos. 63-238111 and 63-2381.
15 etc. Perfluoro (2,
2-Dimethyl-1,3-dioxole)
Monomer (a) and perfluoro (allyl vinyl ether)
And fluorine containing perfluoro (butenyl vinyl ether)
Also by copolymerizing the monomer (b),
A base polymer is obtained. The fluoropolymer is the total weight of the fluoropolymer.
Polymerized unit having a fluorine-containing aliphatic ring structure relative to the combined unit
Containing 20 mol% or more, particularly 40 mol% or more
Is preferable in terms of transparency, mechanical properties, and the like. Specific examples of the fluorine-containing polymer include
Is a repeating unit selected from the following general formulas (1) to (5)
The thing which has is illustrated. In these fluoropolymers
The fluorine atoms of may be partially substituted with chlorine atoms
Yes. [0018] [Chemical 1] In the general formulas (1) to (5), h is 0 to 0.
An integer of 5, i is an integer of 0 to 4, j is 0 or 1, h + i
+ J is 1 to 6, s is an integer of 0 to 5, t is an integer of 0 to 4,
u is 0 or 1, s + t + u is 1-6, p, q, r are
Each independently an integer of 0-5, p + q + r is 1-6,
R¹, R², R³, R⁴, X¹, X²Each independently
H, D (deuterium) F, Cl or CF₃It is. R⁵,
R⁶, R⁷, R⁸Are each independently H, D (deuterium),
F, Cl, C_nF_{2n + 1}, C_nF_{2n + 1-m}Cl_m
O_kOr C_nF_{2n + 1-m}H_mO_kAnd n is 1
~ 5, m is an integer of 0-5, k is an integer of 0-2
R⁷, R⁸May be linked to form a ring. In the present invention, it has a fluorine-containing aliphatic ring structure.
As the fluorine-containing monomer to be used, the following general formula (6) to
The fluorine-containing monomer selected from the compounds represented by (8)
preferable. [0021] [Chemical 2] In the general formulas (6) to (8), X³~ X
⁸Are each independently H, D (deuterium), F, Cl or
CF₃It is. R⁹~ R¹⁴Are independently H, D
(Deuterium), F, Cl, C_nF_{2n + 1}, C_nF
_{2n + 1-m}Cl_mO_kOr C_nF _{2n + 1-m}H_m
O_kN is an integer from 1 to 5, m is an integer from 0 to 5, k
Is an integer from 0 to 2 and R⁹And R¹⁰Connect to form a ring
R¹¹And R¹²Connected to form a ring
Well, R¹³And R¹⁴May be linked to form a ring.
Yes. Specific examples of the compounds represented by the general formulas (6) to (8)
Examples thereof include compounds represented by formulas (9) to (16).
It is done. [0023] [Chemical 3]Fluorine containing two or more polymerizable double bonds
The elementary monomers are represented by the following general formulas (17) to (19).
Are preferred. [0025] [Formula 4] In the general formulas (17) to (19), X⁹
~ X³⁴Are each independently H, D (deuterium), F, C
l or CF₃It is. Represented by general formulas (17) to (19)
Specific examples of the compound to be prepared include the following compounds:
It is done. CF₂= CFOCF₂CF₂CF = CF₂, CF₂= CFOCCl₂CF₂CF = CF₂, CF₂= CFOCF₂CF₂CCl = CF₂, CF₂= CFOCF₂CF₂CF = CF₂, CF₂= CFOCF₂CFClCF = CF₂, CF₂= CFOCF₂CF₂CF = CFCl, CF₂= CFOCF₂CF (CF₃) CF = CF₂, CF₂= CFOCF₂CF (CF₃) CCl = CF₂, CF₂= CFOCF₂CF = CF₂, CF₂= CFOCF (CF₃) CF = CF₂, CF₂= CFOCF₂OCF = CF₂, CF₂= CClOCF₂OCCl = CF₂, CF₂= CFOCCl₂OCF = CF₂, CF₂= CFOC (CF₃)₂OCF = CF₂. In the bulk polymerization in the present invention, the polymerization reaction is carried out.
Fluorine-containing polymer obtained by bulk polymerization, depending on the reactor shape
The polymer has various shapes such as plate, tube, rod, etc.
It can be used as an article. Also obtained by bulk polymerization
Heat-deformation processing, compression molding, extrusion molding of fluoropolymers,
Various types such as plate, tube, and rod by melt molding such as injection molding
It can also be formed into an article having a shape. Made of the present invention
The fluoropolymer obtained by the production method is highly transparent,
The light scattering loss of the fluorine polymer is 100 dB / km or less, 50
dB / km or less or 30 dB / km or less
it can. The transparency obtained by the production method of the present invention
A high fluoropolymer is useful as an optical resin material,
For example, optical fiber or its base material, optical waveguide, optical fiber
For substrate materials for media such as media and compact discs
Available. In addition, because of its excellent chemical resistance, chemical plants
Window material used in the
It can be used for external lamp tubes. In addition, the transparent material obtained by the production method of the present invention is used.
Highly clear fluorine-containing polymer is stabilized by fluorination after polymerization
Is coloring stability high under high temperature and high humidity without treatment?
Have a gel effect as described in JP-A-5-173025.
Has a refractive index profile by radical polymerization
It can also be used to manufacture optical fiber preforms. Soluble in fluorine-containing monomer during bulk polymerization
If so, dos of dyes, high refractive index compounds, conductive compounds, etc.
Mix punts and various organometallic complexes, etc.
Various options are available because it can be uniformly dispersed in the coalescence.
As a matrix material for toelectronic devices
Available. [0031] The following abbreviations are used in the following examples. Ma
Examples 1, 2, and 3 are examples, and examples 4 and 5 are comparative examples.
The PBTHF: perfluoro (2-butyltetrahydrofur
run), PBVE: perfluoro (butenyl vinyl ether), PDD: perfluoro (2,2-dimethyl-1,3-di
Oxole), PFDTBPO: perfluoro (di-tert-butyl
Peroxide), PFBPO: perfluorobenzoyl peroxide. (Example 1) Outer diameter 1.6 mm, inner diameter 1.2 mm
10 g of PBVE, 0.1 g of PFDT
BPO (10 hour half-life temperature 99 ° C.) and 0.04
g of chloroform and freeze degassing using liquid nitrogen
Was repeated three times and then sealed. This is 90 ° C orb
When it was kept in the tank for 2 days, it completely solidified. 1 more
After holding at 10 ° C for 1 day, break the glass tube and remove the polymer.
As a result, a colorless, transparent and tough rod-like solid was obtained.
It was. The obtained rod-like solid (hereinafter referred to as rod A and
The intrinsic viscosity at 30 ° C. in PBTHF is 0.4.
It was 6 dl / g. Also, the rod A is 1 hour at 200 ° C.
When heated for a while, there was no slight bubble formation and colorless transparency was observed.
It was clear. When we measured the weight before and after heating, the weight decreased
Was 0.3%, so the reaction rate of PBVE was 99%
It turned out that it is the above high value. Also, a laser beam having a wavelength of 633 nm is used.
Horizontal deflection component in the scattering angle range of 20 to 120 degrees
And the light scattering intensity of the rod A of the vertical deflection component
The scattering loss was calculated to be 16 dB / km. Ma
The rod A was stored at a temperature of 60 ° C and a humidity of 95% for 30 days.
However, it turned out that there was no coloring at all. As a result,
A is excellent in transparency, and after the polymerization,
Stable under high temperature and high humidity without any stabilization treatment
Confirmed to be a polymer, this polymer is an optical fiber, etc.
It was found to be suitable as an optical resin material. Rod A is set in a mold at 180 ° C., 5
By plastic molding with a load of 0 kg,
I got the There is no bubble formation in this lens,
No coloring was observed. (Example 2) Outer diameter 1.6 mm, inner diameter 1.2 mm
Glass tube with 6 g PBVE, 4 g PDD, 0.5
g PFDTBPO and 0.04 g chloroform
And freeze degassing three times using liquid nitrogen
It was sealed later. Hold this in an oven at 90 ° C for 2 days
As a result, it completely solidified. Hold at 110 ° C for 1 day
After that, the glass tube was broken and the polymer was taken out.
A transparent and tough rod-like solid was obtained. Rod-shaped solid after vacuum drying (hereinafter referred to as rod)
B)) has an intrinsic viscosity of 0.46 in PBTHF at 30 ° C.
dl / g. Heat rod B at 200 ° C for 1 hour
As a result, no foam was observed and the film was colorless and transparent. heating
When measuring the weight before and after, the weight loss was 0.8%.
Therefore, the monomer reaction rate is a high value of 99% or more.
I understood it. Further, the light scattering intensity of the rod B is set to a wavelength 633.
Measured using a laser beam of nm, and the same method as in Example 1
The total scattering loss was calculated to be 35 dB / km.
It was. Rod B is 30 days at 60 ° C and 95% humidity.
It was found that there was no coloring even after storage. to this
Furthermore, rod B is excellent in transparency, and also on polymerization.
High temperature and high humidity without stabilization treatment such as fluorination
The polymer was confirmed to be a stable polymer under
It turns out to be suitable as an optical resin material such as fiber.
It was. Rod B is set in a mold at 180 ° C., 5
By plastic molding with a load of 0 kg,
I got the There is no bubble formation in this lens,
No coloring was observed. (Example 3) Outer diameter 1.6 mm, inner diameter 1.2 mm
Glass tube, 12 g PBVE, 8 g PDD, 0.
2 g of PFDTBPO and 0.12 g of chloroform
Lum is charged and freeze degassing is repeated 3 times using liquid nitrogen
After that, it was sealed. While rotating this glass tube, 9
Hold for 2 days at 0 ° C to polymerize and solidify for approx.
A 20 cm hollow tube was produced. Next, inside this hollow tube
45g of PBVE, 0.45g of PFDTBPO,
And 0.18 g of chloroform, and 2 at 70 ° C.
Hold for 1 day at 100 ° C for 1 day to polymerize and solidify
And then vacuum drying at 90 ° C. for 1 day.
A lad type optical fiber preform was fabricated. This
Reform is heated from the tip using a 250 ° C heating furnace.
Melt a plastic optical fiber with a diameter of 0.6mm
Spinned. Cut back the optical transmission loss of this optical fiber
Measured by the method, 100 dB / wavelength at 780 nm
km, 60 dB / km and 850 nm at 850 nm
50 dB / km, light from visible light to near infrared light
It was confirmed that this is an optical fiber that can be transmitted well. (Example 4) Outer diameter 1.6 mm, inner diameter 1.2 mm
10g PBVE, 0.1g PFBP
O (10 hour half-life temperature 68 ° C.) and 0.04 g
Prepare chloroform and freeze and degas 3 using liquid nitrogen
The tube was sealed after repeating several times. In an oven at 90 ° C
For 2 days, it completely solidified. 110 more
After holding at ℃ for 1 day, break the glass tube and take out the polymer
As a result, a colorless transparent and tough rod-like solid was obtained. The obtained rod-like solid (hereinafter referred to as rod C and
The intrinsic viscosity at 30 ° C. in PBTHF is 0.4.
It was 3 dl / g. Also, the rod C is 1 hour at 200 ° C.
When heated for a while, there was no slight bubble formation and colorless transparency was observed.
It was clear. When we measured the weight before and after heating, the weight decreased
Was 0.4%, so the reaction rate of PBVE was 99%
It turned out that it is the above high value. Same as Example 1
Then, the light scattering intensity of the rod C was obtained, and the total scattering loss was calculated.
However, it was 35 dB / km. The rod C is kept at a temperature of 60 ° C. and a humidity of 95%.
When tube is used, coloring starts to be confirmed from the 7th day, 30th
With eyes, Rod C turned brown. As a result, the rod C becomes
Although it is excellent in transparency, it is fluorinated after polymerization.
If the stabilization treatment is not carried out, the color that is colored under high temperature and high humidity
It was confirmed to be a coalescence. (Example 5) Outer diameter 1.6 mm, inner diameter 1.2 mm
Glass tube with 6 g PBVE, 4 g PDD, 0.1
g of PFBPO and 0.04 g of chloroform.
After charging and repeating freeze degassing three times using liquid nitrogen
Sealed. This was kept in an oven at 90 ° C. for 2 days
However, it completely solidified. Held at 110 ° C. for 1 day
After that, the glass tube was broken and the polymer was taken out.
A bright and tough rod-like solid was obtained. The obtained rod-shaped solid (hereinafter referred to as rod D and
The intrinsic viscosity at 30 ° C. in PBTHF is 0.4.
It was 3 dl / g. Also, the rod D is 1 hour at 200 ° C.
When heated for a while, there was no slight bubble formation and colorless transparency was observed.
It was clear. When we measured the weight before and after heating, the weight decreased
Was 0.9%, so the reaction rate of PBVE was 99%
It turned out that it is the above high value. Same as Example 1
Then, the light scattering intensity of the rod D was obtained, and the total scattering loss was calculated.
However, it was 36 dB / km. The rod D is kept at a temperature of 60 ° C. and a humidity of 95%.
When tube is used, coloring starts to be confirmed from the 7th day, 30th
With eyes, rod D turned brown. As a result, the rod D becomes
Although it is excellent in transparency, it is fluorinated after polymerization.
If the stabilization treatment is not carried out, the color that is colored under high temperature and high humidity
It was confirmed to be a coalescence. [0047] According to the method of the present invention, the thermal stability and chemical properties are improved.
Transparency with excellent stability and no problems such as cloudiness, foaming or coloring
A highly fluorinated polymer can be obtained. This fluorine-containing weight
The coalesced is high temperature and high humidity without any stabilization treatment such as fluorination.
There is no coloration underneath, and white turbidity, foaming, coloration, etc. occur.
Melt molding is possible.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Akihiro Kanda             1150 Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa             Asahi Glass Co., Ltd. (72) Inventor Kuniko Okano             1150 Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa             Asahi Glass Co., Ltd. F-term (reference) 2H050 AA14 AB47Z                 4J015 BA00 BA05                 4J100 AC59Q AR32P AU27P BA02Q                       BB01P BB01Q BB07P BB12Q                       BB13Q BB18P CA01 CA04                       DA62 FA03 FA18 JA33 JA35                       JA36

Claims (1)

What is claimed is: (1) A fluorine-containing dialkyl peroxide polymerization initiator, and the following fluorine-containing monomers (a), (b),
A method for producing a fluorinated polymer, comprising subjecting (c) or (d) to bulk polymerization to obtain a fluorinated polymer having a fluorinated aliphatic ring structure in the main chain. (A) A fluorine-containing monomer having a fluorine-containing ring structure. (B) A fluorine-containing monomer having two or more polymerizable double bonds. (C) A fluorine-containing monomer (a) and a fluorine-containing monomer (b). (D) one or more fluorine-containing monomers selected from fluorine-containing monomers (a) and (b), fluorine-containing monomers (a),
Other fluorine-containing monomers other than (b).