Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
1999-12-15
2002-10-08
Lipman, Bernard (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C524S572000, C525S332900, C525S333100, C525S333200, C525S342000
Reexamination Certificate
active
06462141
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a diene copolymer substituted by silane groups, a composition comprising the same and a process for the preparation of the same. This diene copolymer is modified with silanes and has high solubility in organic solvents and high storage stability. The organic and inorganic hybrid composition comprising the said diene copolymer substituted by silane groups is useful in applications such as white or colored rubber compositions and conductive rubber compositions.
2. Background of the Invention
As chemical modification methods attempting to improve the physical properties of polymer materials including heat resistance, wear resistance, adhesive property and compatibility, copolymerization, block copolymerization or graft copolymerization which provide copolymers with different structural units and other techniques of introducing other functional groups have been developed.
Thus prepared polymers have high elasticity and mechanical properties and thus can be used in a wide range of applications such as tires, shoes, packings, hoses, sheets, impact absorbers, vibration absorbers or additives. However, said methods have restrictions in improving the mechanical properties of thermoplastic elastomers because they have low thermal stability and poor mechanical strength. In order to compensate such drawbacks associated with said chemical modification techniques, research in developing organic and inorganic hybrid materials by blending a polymer with an inorganic material such as silica or a glass fiber have been conducted hereto.
In this context, Korean Patent Laid-Open Publication No. 95-784 discloses the addition of polydimethylsiloxane to a styrene resin. Korean Patent Laid-Open Publication No. 94-19797 discloses the dispersion of polydimethylsiloxane in a styrene type resin composition, thereby remarkably improving wear resistance and impact resistance of the composition. Furthermore, Korean Patent Publication No. 96-1622 discloses a styrene type resin composition comprising (a) 100 parts by weight of styrene type polymer having no functional groups, (b) 0.01 to 30 parts by weight of styrene type polymer having epoxy groups and (c) 1 to 550 parts by weight of inorganic filler surface treated with silane compounds or titanium compounds. However, the organic polymer resin complex prepared by the dispersion of said polydimethylsiloxane or silane compounds has the problems in that firstly, phase seperation may occur due to the lack of covalent bonding between silane compounds and organic polymer resins and secondly, the affinity of silane compounds with inorganic fillers is poor due to the absence of polar groups or hydrophilic groups in silane compounds, thereby decreasing the compatibility of the complex.
Accordingly, in order to develop such organic and inorganic hybrid materials, the modification of polymers by reactive silane group is necessary to improve compatibility between those components. Korean Patent Laid-Open Publication No. 95-704405 discloses the example of the polymerization of hexamethylcyclotrisiloxane at the terminal of living anionic polymer. In this case, the phase isolation between polysiloxane and organic materials was some or less overcome, however since polydimethylsiloxane does not contain any polar groups or hydrophilic groups which would act as functional groups, the affinity with the inorganic fillers is low, thereby the compatibility thereof also decreases.
Therefore, the study of rubber complex wherein diene polymers are substituted by polar silane or silanol groups has become of popular interest. For instance, Takagishi et al. discloses the polymerization method of a vinyl derivative mixture such as butadiene or styrene by the use of Si-containing vinyl monomer such as &ggr;-methacryloxypropyltripropoxysilane in Japanese Patent Laid-Open Publication No. 9-208632, Aug. 12, 1997. The European Patent Publication No. 786493 by Labauze and Gerard discloses that a composition comprising a diene polymer having terminal SiOH groups or OH group-terminated siloxane blocks and silane ZR
1
Si(OR
2
)
3
—n(R
3
)
n
wherein R
1-3
is alkyl, aryl or aralkyl group, Z is amine, polyamine or amine group and n is 0 to 2, has excellent hysteresis properties and S-vulcanizable properties and is suitable for the preparation of tires. However, diene polymers having terminal SiOH groups or alkoxy-terminated siloxanes are prone to gelation and lack storage stability and thus have problems to be industrialized.
Accordingly, there is a need for the development of a novel diene copolymer containing silane groups, which has an improved storage stability and is compatible with inorganic fillers such as silica and/or carbon black.
SUMMARY OF THE INVENTION
The present inventors have made extensive studies in order to overcome the aforementioned problems caused in the preparation of the diene copolymers and to develop a diene copolymer substituted by polar silane groups. As a result, the present inventors have now found that a diene copolymer substituted by silane groups can be prepared by either subjecting a diene copolymer block to epoxidation and reacting the resulting product with silane having amine groups or hydrating the epoxidated diene copolymer and then reacting the resulting product with reactive silanes.
The present inventors have also found that the composition prepared by adding silica, alkoxysilane or derivatives thereof and other additives to thus prepared diene copolymer is useful for the preparation of white or colored tires and may be applied as a conductive rubber complex if it is mixed with conductive carbons or carbon fibers. In particular, the present inventors have discovered that thus prepared composition may be applied onto a substrate or a mold, which is then heated at a temperature from room temperature to 170° C., resulting in film composite or a molded article filled with organic and inorganic hybrid composite or inorganic particles. The present invention is attained on the basis of these findings.
DETAILED DESCRIPTION
Accordingly, the present invention relates to alkoxysilane-substituted diene copolymer of the formula (1)
wherein
R
1
is H, a lower alkyl having carbon atoms less than 10, a fluoro group or unsubstituted or substituted benzene group,
R
2
has the same meaning as R
1
or is ether and/or ester having carbon atoms less than 10, or alkyl group substituted by halogen, hydroxyl group, vinyl group and/or acrylic group,
R
3
is W[(C(R
1
)
2
]
n
wherein W is CO or CONHCO and n is a number from 0 to 10,
x, y and z, each, independently of the other, are a number more than 0 and represent a weight ratio, and m is an integer from 0 to 3, provided that y block may comprise a partially hydrogenated CH
2
CH(R
2
)CH(R
2
)CH
2
.
The alkoxysilane-substituted diene copolymer of the formula (1) may be prepared by reacting a diene polymer of the formula (2)
wherein R
1
, R
2
, x, y and z have the same meaning as defined in the formula (1), or the formula (3)
wherein R
1
, R
2
, x, y and z have the same meaning as defined in the formula (1), with a silane compound of the formula (4)
(R
1
)
m
Si(OR
1
)
3−m
[C(R
1
)
2
]
n
R
4
wherein R
1
, m and n have the same meaning as defined in the formula (1) and R
4
is halogen, hydroxyl group, vinyl group, acrylic group, COOH, NCO or NH
2
.
The diene copolymer substituted by silane has good solubility in organic solvents and excellent adhesive property to a substrate and does not exhibit gelation after long time storage at room temperature due to its good storage stability.
The method for the preparation of the diene copolymer of formula (2) substituted by 1 to 70% of epoxy group is known and for example, can be obtained by reacting a diene copolymer with hydrogen peroxide or 3-chloroperoxy benzoic acid (refer to WO97/02296, WO98/28338, Japanese Patent Publication Hei 10-1564 and Polymer, 1987, 28, 1977).
The method for the preparation of the diene copolymer of formula (3) wherein the diene copolymer block is su
Cho Hyung-suk
Kim Eun-Kyoung
Kim Young-Pil
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