JPH032243A - solid polymer material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to solid polymeric materials.

(Prior Art) A conventional method is known in which a monomer or prepolymer is injected into a polymeric material and polymerized to obtain a polymeric material. For example, JP-A No. 62-33524 discloses that monomers or prepolymers are injected into substituted polyacetylene to make it into a polymer, and JP-A No. 62-235318 discloses that a polymer with a three-dimensional structure is made into a three-dimensional polymer. A method is described in which a monomer containing a crosslinking agent is added, and then three-dimensionalization is performed. Although it is known to perform a polymerization reaction by occluding a monomer in a polymer, there has been no such reaction using an acrylic polymer and a styrene monomer.

(Problems to be Solved by the Invention) An object of the present invention is to provide a highly functional solid polymer substance.

(Means for Solving the Problems) The present invention uses an acrylic polymer as a host polymer, contacts the host polymer with a styrene monomer as a guest, polymerizes the guest in the host polymer, or further provides IPN The present invention relates to a solid polymer substance characterized by having a structure of

In the present invention, commonly known acrylic polymers can be used, such as single or copolymers of the following acrylic monomers.

The acrylic monomer is not limited to Ill, but includes mono- or polyfunctional ones, preferably, for example, methyl methacrylate (M M A ), ethyl methacrylate (E M A ), butyl methacrylate (BMA),
2-hydroxyethyl methacrylate (HEMA), 3
-(tritoxysilyl)propyl methacrylate (M
SPM), 2-(phenylphosphoryl)ethyl methacrylate) (pbenyl-P), 2-hydroxy-
3-(β-captoxy)propyl methacrylate) (HN
PM), N-phenyl-N-(2-hydroxy-3-methacryloxy)propylglycine (NPC-GMA),
Ethylene glycol dimethacrylate (EDMA, or IG), diethylene glycol dimethacrylate (Di
EDMA), triethylene glycol dimethacrylate)
(TriEDMA), 1,4-butanediolnomethacrylate) (1,4BuDMA), 1,3-butanediolnomethacrylate) (1,3-BuDMA), 2,2-
Bis[4-(2-human axy-3-7tacryloxybropoquine)phenyl]propane (Bis GMA), 2
, 2-bis(4-7tacryloxyphenyl)propane (
BPDMA), 2,2-bis(4-7 tacryloxyethoxyphenyl)propane (Bis-MEPP), 2,2
-Bis(4-methacryloxypolyethoxyphenyl)propane (Bis-MPEPP), -(butyl methacrylate)trimethylhexamethylene diurethane (UDMA)
, trinotyolpropane trinotacrylate (T
MPT), CI+,=C(CI,)COOCH2CF, (3F
MA), CIl□=C(CH3)COOCII2CF
zCFz (5F M A ), Cl2=C(CHs
) COOCHz (CFz)2cFs (7F M A
), e112=C(C11,)C00CI+2(CF
2), CF211 (8FMA), their corresponding 7 acrylates, and each α-fluoroacrylate.

Furthermore, all commonly known styrenic monomers can be used, and specific examples include homopolymers of styrene, α-methylstyrene, methylstyrene, dichlorostyrene, and combinations of these with 7-crylonitrile, butadiene,
Ethyleneglyfur dimethacrylate (IG), 1
．． 4-butanol methacrylate) (1,4BuD
MA), diethylene glycol dimethacrylate (Di
EDMA), triethyleneglyfur dimethacrylate (TriEDMA), 1,3-butanolnomethacrylate (1,3-BuDMA), 2,2-bis(4-(2-hydroxy-3-methacryloxy) Examples include copolymers with propoxy)phenyl]propane (Bis-GMA), )limethylolpropane trinotacrylate (TMPT), and the like.

In the present invention, the above-mentioned acrylic polymer is used as a host polymer, a styrene monomer is brought into contact with the host polymer as a guest, and the guest is polymerized in the host polymer, or further converted into IPN to form a target solid. Obtain a polymeric material with a shape.

At that time, when destomotsmer is brought into contact with the host polymer,
Usually, the former dissolves or swells in the latter, or the latter impregnates in the former.

Further, as a method for polymerizing the guest polymer, known polymerization methods for styrene monomers can be used, but photopolymerization and thermal polymerization are preferred.

In the present invention, when the polymerization reaction is carried out by heat polymerization, for example, by heating at a temperature of about 40 to 100°C for about 10 to 150 minutes, or when carried out by photopolymerization, for example, by irradiating with visible light or ultraviolet rays for several minutes. It is preferable to polymerize for minutes to several tens of minutes.

In the present invention, the above-mentioned polymeric substance is
enetrating Polymer N e
It also includes those that have been converted into ``work''. IPN conversion was originally 2
Seed chain polymer in liquid form! ! ! It is a polymer formed by mixing in a solution (or a solution is possible), crosslinking both or one of them, and entangling the molecular chains with each other. When this method is utilized in the present invention, several anomalous methods are used. That is, for example, in the first method, a polymer substance is formed into a film in advance, and a monomer forming a guest polymer is injected into the film in a gas phase, or the film is immersed in a solution containing the monomer, and then the monomer is injected into the film. After that, it is polymerized or crosslinked by heating or light irradiation.

The second method, similar to normal IPN formation, involves dissolving a polymeric substance in a suitable solvent, mixing and reacting the guest component with this, casting the solution to form a film, and heat-treating as necessary. etc. Other methods can also be used.

In order to proceed with IPN formation, it is necessary to carry out crosslinking, for example, by using an acrylic polymer that has been crosslinked in advance by a conventional method, or by incorporating a monomer having a polyfunctional group into the monomer system. In addition, crosslinked polymers are obtained by copolymerization, and the resulting uncrosslinked polymers are treated with organic peroxides, radiation, ionic compounds, and other lanocal sources, ion sources, etc. in a manner suitable for the polymer. Examples include a method of crosslinking.

The solid polymeric substance of the present invention has excellent low hygroscopicity, and
It has excellent transparency, impact resistance, dimensional stability, and biocompatibility, so it can be used not only for various molded products, but also for medical materials, optical materials,
Used as a highly functional material such as various separation membrane materials.

In actual use, methyl ethyl ketone (MEK)
), the intrinsic viscosity measured at 35°C is 0.05 to 1. O
d1/g is preferable, and if necessary, filler,
Various additives such as pigments, surface modifiers, and conductive substances can be used.

(Example) Examples will be described below.

Example 1 To a monomer mixture of 15 g of styrene monomer (St) and 5 g of ethylene glycol dimethacrylate (IG), 0.5 wt% of can-7-arquinone (C
Q) and trimethylaminoethyl methacrylate) (DMA
After dissolving 20 g of polyethyl methacrylate (PEMA) and homogenizing the solution, visible light was irradiated for photopolymerization.

The Vickers hardness of the obtained polymer material was 9.3 Hv (2
5°C). Further, the density measured by the density gradient method at 20°C was 1.02 g/am'. In addition, Shimadzu Corporation's Thermal Analyzer DT-
The starting temperature (TD) of thermal decomposition γ was 280°C, as measured using No. 30 in a nitrogen atmosphere at a heating rate of 10°C/min. Incidentally, there was a weight decrease of about 3 to 4% at 139°C. TD of PEMA is 219℃, about 3-4% at 149℃
There was some weight loss.

Example 2 A polymeric substance was obtained in the same manner as in Example 1 except that 10 g of StlOg and 1G were used as monomers.

The Vickers hardness of the obtained polymer material is 11.3 l-1
ivy at v (25℃). Also, the density (20°C) l! 1.
03g/cm) and ivy, and TD Ha at 232°C,
There was a weight loss of about 3 to 4% at 142°C.

Example 3 For 15 g of styrene moamer (SL) and 5 g of ethylene glycol dimethacrylate (IG), PEMA
A polymeric substance was obtained in the same manner as in Example 1, except that 40g of .

The Vickers hardness of the obtained polymeric material was 12.7Hv (
25℃), and the density (20℃) was 1,01g7
It was cm3. Incidentally, the TD was 249°C, and there was a weight loss of about 3 to 4% at 127°C.

Example 4 PEMA was added to 18 g of styrene monomer (st) and 28 g of 1,4-butanol dimethacrylate.
A polymer material was obtained in the same manner as in Example 1 except that No. 08 was used.

The Vickers hardness of the obtained polymeric material was 6.5H■ (2
5°C). Also, the density (20℃) is 1,014/
cm'. Note that TD was 225°C.

Example 5 20 g of PEMA was dissolved in a monomer mixture of 9 g of styrene and 1 g of 5FMA, and photopolymerization was performed in the following manner to obtain a polymerized cured product. That is, 0.5 wt% of can-7-arquinone (CQ) and trimethylaminoethyl methacrylate (DMAEMA) were added to the total amount of Moamer,
Polymerization was performed by irradiating visible light for 10 minutes at room temperature.

The Vickers hardness of the obtained polymer material is 4.11-[v
(25°C). Also, the density (20℃) is 1.03g
/cken], the intrinsic viscosity η measured at 35°C in the solvent MEK with an U bbe 1ohde type viscometer is 0,567 d.
f/g. In addition, η of PEMA measured in the same manner
is 0,688. It was Jl/g.

(that's all) Sender: Daikin Emata Co., Ltd. Representative Patent Attorney 1) Iwao Mura

Claims (1)

[Claims] (1) It has a structure in which an acrylic polymer is used as a host polymer, a styrene monomer is brought into contact with the host polymer as a guest, and the guest is polymerized in the host polymer or further converted into IPN. A solid polymer substance.