JP2582524B2 - Crosslinked organosilicon polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to polymers of certain siloxanes and polysaturated hydrocarbons. Hydrosilane (ie, = Si
-H) It has long been known that compounds having a functional group can react with alkenes having vinyl (terminal) unsaturation to form alkylsilanes. The simplest example of this reaction is the addition of trichlorosilane to ethylene, producing ethyltrichlorosilane. This exothermic reaction is catalyzed by a platinum halide compound and substantially
Easily progresses to 0% conversion.

This reaction, known as "hydrosylation" or "hydrosilylation", has been found to be effective with a number of vinyl compounds. Similarly, other silanes such as dialkylsilanes, halo-alkylsilanes, and alkoxysilanes have been found to perform this reaction as long as they have the requisite = Si-H groups. A number of organosilicon polymers have been disclosed in the prior art, which are in fact vinyl addition polymers controlled at silicon-containing moieties. The polymer in some cases occurs via conventional olefin polymerization routes without the use of hydrosilation. The silicon-containing sites are then present as polymerization regulators. Examples of such polymerizations include, for example, U.S. Pat.
No. 125,554, No. 3,375,236, No. 3,8
Nos. 38,115, 3,920,714 and 3,
No. 929,850.

[0003] To produce highly crosslinked thermoset polymer, some examples the polymerization takes place by reaction between a vinyl silane _{(= Si-CH = CH 2} ) a compound having a group and hydrosilane (= Si-H) groups Have been reported. Examples of this type of reaction include U.S. Pat. Nos. 3,197,432, 3,197,433 and 3,438,936. Each of these patents teaches the preparation of polymers from vinylalkylcyclotetrasiloxanes and alkylcyclotetrasiloxanes having 2 to 4 silane hydrogen atoms.

[0004] It is desirable to provide new polymeric organosilicon polymers which have excellent physical, thermal and electrical properties and outstanding water resistance and which can be used to produce molded articles. According to the present invention, the crosslinked or crosslinkable organosilicon polymer is alternated from polycyclic hydrocarbon groups and cyclic polysiloxane or siloxysilane groups linked via carbon-silicon bonds. It is a feature.

Preferably, the organosilicon polymers of the present invention comprise (a) a cyclic polysiloxane or tetrahedral siloxysilane containing at least two hydrosilane groups, and (b) at least two non-aromatic carbon- A reaction product with a polycyclic polyene having a carbon double bond, and wherein the ratio of the carbon-carbon double bond in the ring of (b) to the hydrosilane group in (a) is greater than 0.5: 1 1.8: 1 and at least one of (a) and (b) is 2
Having more than one reactive site (the reactive site is (a)
And a carbon-carbon double bond in the ring of (b)).

If a thermoset polymer is desired, the ratio of the carbon-carbon double bond in (b) to the hydrosilane group in (a) is more preferably from about 0.7: 1 to about 1.3: 1. Ranges from about 0.8: 1 to about 1.1: 1. The alternating groups form a crosslinked thermoset structure. If a thermoplastic polymer is desired, the ratio of the intra-ring carbon-carbon double bond in (b) to the hydrosilane group in (a) should be 0.
Range from greater than 5: 1 to about 0.7: 1 or about 1.
It ranges from 3: 1 to 1.8: 1.

Further, according to the present invention, a method for producing an organosilicon polymer of the present invention comprises the steps of:
(A) a cyclic or tetrahedral polysiloxane containing at least two hydrosilane groups and (b) a polycyclic polyene (provided that the ratio of the carbon-carbon double bond in (b) to the in-ring hydrosilane group in (a) is Greater than 0.5: 1 and 1.8: 1
And at least one of (a) and (b) has more than two reactive sites] and heating the polymer to maximize cross-linking. .

[0008] Any cyclic polysiloxane or tetrahedral siloxysilane having two or more hydrogen atoms bonded to silicon participates in the reaction. Cyclic polysiloxanes useful in forming the products of the present invention have the general formula

Embedded image (Where n is an integer of 3 to 20, R is hydrogen, a saturated substituted or unsubstituted alkyl or alkoxy group, a substituted or unsubstituted aromatic or aryloxy group ,
In each case, hydrogen is the least silicon atom in the molecule.
At least two must be present ).

The tetrahedral siloxysilane has the general formula

Embedded image (However, R is as defined above, one of the field
Hydrogen is at least two of the silicon atoms in the molecule
Must be present ).

Examples of the reactant having the formula (I) include, for example, trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, pentamethylcyclopentasiloxane, hexamethylcyclohexasiloxane, tetraethylcyclotetrasiloxane, cyclotetrasiloxane, Examples include tetraphenylcyclotetrasiloxane, tetraoctylcyclotetrasiloxane and hexamethyltetracyclosiloxane.

The most commonly occurring members of this group are tetra, penta, and hexacyclosiloxane, with tetramethyltetracyclosiloxane being preferred. However, in most cases, this material is a mixture of many compounds, where n can vary widely. Generally, commercially available mixtures are up to about 20% (of as little as 2% in relatively pure form) of low molecular weight linear methylhydrosiloxanes, such as heptamethyltrisiloxane, octamethyltrisiloxane, and the like.

Examples of reactants having formula (II) include, for example, tetrakisdimethylsiloxysilane, tetrakisdiphenylsiloxysilane, and tetrakisdiethylsiloxysilane. Tetrakisdimethylsiloxysilane is best known and is the preferred one in this group. Cyclic polyenes that can be used are polycyclic hydrocarbon compounds having at least two non-aromatic carbon-carbon double bonds in the ring. Examples include the following compounds, cyclopentadiene, methyldicyclopentadiene, cyclopentadiene oligomer, norbornadiene, norbornadiene dimer, hexahydronaphthalene, dimethanohexahydronaphthalene, and substituted derivatives of any of these.

This reaction proceeds easily in the presence of a platinum-containing catalyst. Metals, salts and complexes of Group VIII elements can also be used. From both reactivity and cost,
Preferred catalysts are chloroplatinic acid _{(H 2 PtCl 6 · 6H 2} O). 0.0005 to about 0.5, based on the weight of the monomer
A catalyst concentration of weight percent helps smooth and substantially complete polymerization. In some cases, other platinum compounds such as PtCl ₂ and dibenzonitrile platinum dichloride can also be advantageously used. Pt / C is also effective in performing high temperature polymerization. Other useful platinum catalysts are described, for example, in US Pat.
No. 20,972, No. 3,715,234 and No. 3.1
No. 59,662. Advances in Organometalli for a thorough study of hydrosilation catalysts
c Chemistry, vol. 17, p. 407 et seq.
This polymerization reaction can be accelerated thermally or by the addition of radical generators such as peroxides and azo compounds.

The polymer of the present invention is a homopolymer, ie, 1
May be the reaction product of one hydrosilane-containing reactant with one polycyclic polyene, or they may be prepared from a plurality of hydrosilane-containing reactants by one or more polycyclic polyenes. It will be apparent to those skilled in the art that it may be a polymer. Any combination of silane-containing compound and polycyclic polyene is possible, as long as the specific ratio of> C = <group to = Si-H group is satisfied. One example of a crosslinked thermoset polymer according to the present invention is the reactant of 1 mole of tetrakisdimethylsiloxysilane and 2 moles of norbornadiene, which, when fully cured, has the following structural formula for the 2,5 isomer: [Also, there can be 2,6 isomers].

[0015]

Embedded image

By selecting the reactants, reactant concentrations and reaction conditions, it is possible to produce the polymers of the present invention having a wide range of properties and physical forms. Therefore,
It has been found that it is possible to produce sticky solid elastic materials, as well as tough glassy polymers. The thermoset polymers of the present invention have a range of uses depending on their physical form. Sticky solids are useful as tackifiers in pressure sensitive adhesives and as pressure sensitive adhesives.
They are also useful as in-situ curable, structural adhesives that form strong bonds due to the high affinity of the hydrosilane-derived silanol groups for polar metal surfaces, especially oxidized metal surfaces. Since the elastomeric material is cured in situ and is not water sensitive, it creates an excellent potting compound for electronic components.

The thermal properties of these thermoset polymers are also prominent. The glass transition temperature (Tg) of a fully cured thermoset polymer is about 200 ° C. or higher. Thermal stability is excellent, with a weight loss of usually less than 10% at 500 ° C. during thermogravimetric analysis. 1100 in the air
At 50 ° C., about 50% residue remains. The thermoset polymer is fire resistant and burns very slowly when exposed to a flame. A particularly striking property of these thermoset polymers is that they are substantially insensitive to water. They have been found not to be affected by boiling water after a long period of time.

The thermoset polymer also has resistance to oxidation to ultraviolet radiation at room temperature. 20
Above 0 ° C., oxidative cross-linking of the silicon portion of the molecule occurs, resulting in the formation of a dark silicon outer layer. This oxidized outer layer appears to prevent oxidative degradation of the polymer. Rigid glassy thermoset polymers are useful in many applications where glass is currently used, for example, lining water heater tanks. The insensitivity of these thermoset polymers to water and their high temperature properties are ideal for this type of application. In addition, the impact resistance of glass-filled polymers is not extraordinary, but is better than glass, so that lined tanks can withstand stricter transport, handling and installation conditions than glass.

The rigid glassy thermosetting polymer is thermally decomposed when heated to 1000 ° C. or higher. This heat resistance makes them useful as refractory and ablation materials. The thermoplastic polymer of the present invention generally has a temperature of about 60 ° C.
Shows a melting point in the range of about 130 ° C. However, when post-cured at temperatures above 200 ° C., certain (eg,
1.45: 10 with> C = C <: = Si-H equivalence ratio) exhibit elastic properties, and in some cases have a relatively high softening point after post-cure or Shows curability.

The thermoplastic polymers of the present invention range from sticky to hard, non-sticky solids having a low melting point.
Certain of these polymers (eg, 1.45:
1.0 having> C = C <: = Si-H equivalent ratio)
At relatively high temperatures (200
Until heated to ~ 300 ° C), it exhibits thermoplastic behavior (melt flow). These can be considered as thermoplastic-thermoset polymers. These materials are coated on a substrate as a powder, melt, or solution and cured to form a polymer having a predominantly thermosetting behavior (eg, from about 0.7: 1 to about 1.3:
A glass transition point which is somewhat lower than that of (1) having> C = C <: = Si-H equivalent ratio) can be obtained.

Several methods can be used to produce the novel thermoset polymers of the present invention. In the first method, the correct relative ratios of reactants and platinum catalyst are simply mixed to a temperature at which the reaction is initiated, and then maintained at appropriate temperature conditions to substantially complete the reaction (typically, For> C = C <: = Si-H equivalence ratio of about 1: 1
70-80% of the hydrosilane groups are consumed). Normal,
As the molecular weight of the polymer increases, periodic temperature increases are desirable to drive the reaction. The reaction is carried out in a conventional manner, at least until sufficient cross-linking has occurred to fix the desired shape of the polymer. Next, if necessary, the mold can be removed from the mold and post-heat treatment can be continued to further proceed the reaction toward completion. If the two double bonds in the diene molecule are equivalent in reactivity and cross-linking begins shortly after the start of the reaction, then this relatively simple method is a more manageable method.

The hydrosilation reaction of polycyclic polyene rings with carbon-carbon unsaturation and hydrosilane groups is a primary polymerization and cross-linking mechanism, but other types of polymerization and crosslinking occur as the cure temperature increases. May be. These include, for example, oxidative crosslinking, free radical polymerization (olefin addition reaction) and condensation of silanols forming siloxane bonds.

The initial product of the reaction at relatively low temperatures is a flowable thermoset liquid prepolymer or a liquid thermoset liquid, even if the ratio of> C = C <to = Si-H is otherwise suitable for cross-linking. It is often an oligomer (hereinafter referred to as "prepolymer"). The liquid prepolymer is analogous to the so-called B-stage resin encountered in other thermoset products and can be recovered and then transferred to a mold for curing.
These viscous flowable liquid prepolymers are stable at room temperature for various times, but upon reheating to the appropriate temperature,
When the polymerization is carried out substantially immediately, it is cured to the same type of thermoset polymer produced.

After the initial exotherm, the B-staged prepolymer cools the reactants to about 30-65 ° C. and holds at that temperature for several hours, then undergoes a transition to a glassy crosslinked thermoset polymer. The reaction is interrupted by removing heat until complete. This viscous flowable liquid reacts about 30-50%,
The viscosity changes accordingly. In practice, by monitoring the increase in viscosity, it is possible to select the point at which the polymerization should be interrupted, to suit its purpose.

Thermoplastic polymers can be made substantially similar to thermoset polymers. That is, they are simply
It may be prepared by mixing the correct ratio of reactants and catalyst and bringing to a temperature at which the reaction is initiated. The reaction can then proceed to completion using appropriate temperature conditions. Again, it is preferred that the temperature be raised periodically as the molecular weight of the polymer increases.

The initial product of the reaction is a viscous, flowable liquid, which can be heated to complete the reaction, as described above. However, as long as the obtained polymer is thermoplastic, the polymer can be heated, molded and cooled to form a molded product, and thus the reactant is generally used as a B-stage prepolymer or oligomer as described above. You don't need to keep it in shape. The thermoplastic polymer is ground and transported to a molder where it is heated to form a molded article. Thus, a liquid prepolymer, oligomer or polymer intermediate can be formed as described above,
In most cases these thermoplastic polymers are solid, for example,
It is preferred to produce in powder form ready for use in the molding operation.

There are a number of options for incorporating additives into the polymer. Additives such as fillers and pigments are easily formulated. Carbon black, vermiculite, mica, wollastonite, calcium carbonate, sand, glass spheres, glass beads, ground glass and waste glass are examples of fillers that can be included. Fillers serve as reinforcements or as fillers and extenders to reduce the cost of the molded article. Glass spheres are useful for making low density composites. When used, the filler is about 80%
Can be present in amounts up to. Stabilizers and antioxidants are useful in maintaining the storage stability of the B-stage material and the thermo-oxidative stability of the final product.

Glass or carbon fibers, such as graphite fibers, are very well wetted by the liquid prepolymer, making the polymer an excellent matrix material for high strength composite structures. Thus, the prepolymer can be charged into a mold containing the required staples or continuous filaments and cured to form the desired composite structure. Fibers in the form of a woven fabric can also be used. Alternatively, the solid thermoplastic polymer may be melted and poured over the fibers and heated to form a composite, or a thermoplastic polymer powder may be blended with the fibers and then heated to form a composite. May be formed. The polymer fiber reinforced composites of the present invention can contain 80%, preferably 30-60%, by weight of the fibrous reinforcement and, when fully cured, typically have very high tensile and flexural strength. And excellent impact strength. It can also be used with other types of fibers, such as those of metals, ceramics and synthetic polymers.

The glass-filled thermoset product polymerized to a tough glassy state is characterized by high physical properties, ie, high modulus and high tensile strength and good bending properties. They are refractory, burn very slowly when exposed to a flame, and self-digest when the flame is removed.

Next, examples will be described to explain the present invention, but the present invention is not limited to these examples. Example 1 This example illustrates the preparation of a novel thermoset polymer according to the present invention by reacting dicyclopentadiene with tetrakisdimethylsiloxysilane using a 1: 1 ratio of carbon-carbon double bonds to hydrosilane groups. The reaction vessel was dried, capped using a stream of N ₂ and a heat gun (300 ° C. pot temperature) and placed in a nitrogen flushed glove bag while hot. After equilibration, the tube was tared on the balance, returned to the glove bag, and the PtCl ₂
0.027 g was charged. 1.27 cm (1 /
The reaction vessel was capped by inserting a 2 ") magnetic stirrer. Dicyclopentadiene (2.68 g, 0.02 mol) was charged to the reaction vessel using a 5 cc syringe. The mixture was stirred. ₂ at 90 ° C with gentle N ₂ purge
Heating was performed for a time to form a catalyst complex. The sample was cooled to 35 ° C., tetrakisdimethylsiloxysilane (3.28 g, 0.01 mol) was charged by syringe, and the reaction mixture was returned to a 90 ° C. oil bath. After stirring for about 2 minutes, the sample foamed and turned dark. Sample in oil bath 1
Further heating to 65 ° C. for 3 hours, during which polymerization occurred as the sample continued to thicken. Further 1/2 hour 190
The heat treatment was performed at 215 to 235 ° C. for 3 hours. The sample was cooled and removed from the reaction vessel. The final sample was dark rubbery and tough.

Example 2 This example illustrates a novel thermoset polymer according to the invention, namely:
Figure 3 illustrates the production of a film consisting of the reaction product of tetramethylcyclotetrasiloxane and norbornadiene using a ratio of carbon-carbon double bonds to hydrosilane groups of 1.
Chloroplatinic acid (0.003) was added to the reaction vessel under a nitrogen sweep.
0 g, 200 ppm). The reaction vessel was capped and the reaction vessel sealed with a syringe at 8.57.
g (0.035 mol) of tetramethylcyclotetrasiloxane and 6.43 g (0.070 mol) of norbornadiene were charged. The contents of the reaction vessel were blanketed under nitrogen and stirred at 50 ° C. with heating for 2.5 hours. Two hours later, the initial yellow color disappeared and the viscosity of the liquid increased. After 2.5 hours at 50 ° C., the reaction mixture was diluted by injecting 15 ml of dry xylene and filtered through paper 41 to remove insoluble black catalyst residues. The resulting polymer contained 10 to 50 ppm of Pt (X-ray analysis).

A film of the filtered toluene solution, 0.38 mm (15 mil) in thickness, was poured onto a glass plate using a doctor blade, and xylene was evaporated overnight. The film on glass was heated in a stream of nitrogen at 100 ° C. for 70 hours, then at 200 ° C. for 4 hours. The films were immersed in water at room temperature for several hours and they were peeled from the glass. These films showed no significant absorption at 220-800 nm by visible / uv analysis.

EXAMPLE 3 This example illustrates the preparation of B by partially reacting dicyclopentadiene and tetramethylcyclotetrasiloxane (1: 1 ratio of carbon-carbon double bonds to hydrosilane groups).
Figure 3 shows the preparation of a molded glass cloth reinforcement comprising a novel thermoset polymer according to the present invention in which a step prepolymer is prepared, the B step prepolymer is poured into a mold and heated to complete the polymerization.

750 m dry in N ₂ filled glove bag
1 chloroplatinic acid (0.0101 g) was charged into the reaction vessel, and the reaction vessel was sealed. Dry dicyclopentadiene (26.44 g, 0.2 mol) was charged by syringe. The mixture was allowed to form for 1 hour heated to dicyclopentadiene _{/ H 2 PtCl 6 · 6H 2} O catalyst complex at 55 ° C.. When dry tetramethylcyclotetrasiloxane (24.05 g, 0.10 mol) was added stepwise at 56 ° C, an immediate exotherm occurred and the temperature was 174 ° C.
It became. The mixture was cooled to 64-65 ° C and kept at that temperature for 1.5 hours. Si ²⁹ NMR shows that the hydrosilation reaction is about 50% complete at this time. The low viscosity product was removed from the reaction vessel by syringe and poured into a Teflon-coated mold having a glass cloth completely filling the mold cavity. The resin in the mold was degassed in a vacuum oven at 60 ° C. under a slight vacuum.
The vacuum on the aspirator was manually controlled to prevent the resin from foaming from the mold. The mold was heated in an oven at 68 ° C for 18 hours, then at 140-150 ° C for 3 days. Cool the oven slowly, remove the mold and remove the very hard toughness of 12.7cm x 12.7cm x 0.32cm (5 ")
× 5 ″ × 1/8 ″) plaque was obtained. Rheology, tensile and flexural properties were measured by cutting samples and the following data were obtained:

60% glass cloth 40% tetramethylcyclotetrasiloxane / dicyclo
Pentadiene (1/2) tensile strength 1.64101 kPa (2
3,800 psi) Tensile modulus 8.27 × 10 ⁶ kPa
(1.2 × 10 ⁶ psi) Elongation% (break) 2.2 Flexural strength 278 558 kPa (40,
400psi) Bending modulus 15.17 × 10 ⁶ kPa
(2.2 × 10 ⁶ psi) Rockwell R Hardness 119 Glass Transition Temperature (Rheometrics) 160 ° C. Notched Izod Impact 10 ft / lb Notch Heat Deflection Temperature [1820.28 kPa (264 psi)]> 300
° C

Example 4 This example illustrates the preparation of a novel thermoset polymer according to the present invention by reacting norbornadiene with tetramethylcyclotetrasiloxane using a carbon-carbon double bond to hydrosilane group ratio of about 1: 1. Show. In dry N ₂ sparge the reaction vessel to insert the stir bar _{H 2 PtCl 6 · 6H 2 O} 0.0021g
Was charged. The container was capped and charged with 4.47 g (0.05 mol) of norbornadiene. The resulting mixture was stirred at 60 C for 30 minutes. Upon addition of tetramethylcyclotetrasiloxane (5.83 g, 0.024 mole), the reaction mixture gelled after about 3 hours. Remove the sample from the reaction vessel and at 150 ° C. for 16 hours,
Cured at 250 ° C. for 2 hours and 280 ° C. for 16 hours to give a brown glassy solid.

Example 5 This example illustrates the preparation of a novel thermoset polymer according to the present invention by reacting dicyclopentadiene with methylcyclotetrasiloxane using a carbon-carbon double bond to hydrosilane group ratio of about 1: 1. Show. Following the general procedure in Example 4, dicyclopentadiene (20.12 g, 0.152 mol) and H
_{2 PtCl 6 · 6H 2 O (} 0.0076g) and the mixture heated (60 ° C.) tetramethylcyclotetrasiloxane (18.1 g, 0.075 mol) under was added. The reaction mixture exothermed to 186 ° C. 30 seconds after the addition of tetramethylcyclotetrasiloxane. The reaction mixture is
The mixture was stirred at 0 ° C for 16 hours, at 70 ° C for 24 hours, and at 150 ° C for 5 hours. Pour this mixture into an aluminum pan,
12 hours at 200 ° C, 2 hours at 225 ° C, 2 hours at 250 ° C
Curing at 280 ° C. for 16 hours resulted in a brown glassy solid.

The thermal stability of the polymers of Examples 4 and 5 is shown in the following table.

[Table 1]

EXAMPLE 6 This example illustrates a novel molded thermoset polymer according to the invention for reacting dicyclopentadiene with methylcyclotetrasiloxane using a carbon-carbon double bond to hydrosilane group ratio of about 1: 1. The production of is shown. Following the general procedure of Example 4,
Dicyclopentadiene (54.71g, 0.414 mol) and _{H 2 PtCl 6 · 6H 2 O} (0.0209g) tetramethyl heated (70 ° C.) below into a mixture of cyclotetrasiloxane (49.76g, 0. 20 mol) was added. The reaction mixture exothermed to 170 ° C. 30 seconds after the addition of tetramethylcyclotetrasiloxane. The reaction mixture is
Stirred at 130 ° C. for 6 hours and poured into Teflon-coated molds. This sample was cured at 150 ° C. for 16 hours to obtain an opaque glassy solid.

Example 7 This example illustrates the preparation of a molded glass cloth reinforcement made of a novel thermoset polymer according to the present invention. A B-stage prepolymer was prepared by partially reacting dicyclopentadiene with tetramethylcyclotetrasiloxane in an amount such that the ratio of carbon-carbon double bonds to hydrosilane groups was 1.1: 1. Next, the B-stage prepolymer was poured into a mold containing a glass cloth and heated to complete the polymerization.

Following the general procedure in Example 4, dicyclopentadiene (34.4 g, 0.26 mol) and H ₂ PtCl _6.
Heat to a mixture with 6H ₂ O (0.0126 g) (55 ° C.)
Lower tetramethylcyclotetrasiloxane (28.6 g,
0.12 mol) was added. The reaction mixture exothermed 30 seconds after the addition of tetramethylcyclotetrasiloxane, resulting in 184
° C. The reaction mixture was stirred at 80 ° C. for 2 hours and then transferred to a Teflon-coated mold containing 50.9 g of glass fiber fabric. The sample was cured for 12 hours at 130 ° C., 160 ° C. for 8 hours, and 180 ° C. for 16 hours to give an opaque glassy plaque containing 60.7% by weight glass cloth. The plaques were further cured in an oven flushed with N ₂ at 200 ° C., 250 ° C. and 310 ° C. for 4 hours each.

Example 8 This example illustrates the preparation of B by partially reacting dicyclopentadiene and tetramethylcyclotetrasiloxane (1: 1 ratio of carbon-carbon double bonds to hydrosilane groups).
Figure 4 shows the preparation of a molded opaque solid plaque of the novel thermoset polymer according to the present invention in which a staged prepolymer is prepared, the B-staged prepolymer is transferred into a mold and heated to complete the polymerization.

Following the general procedure in Example 4, dicyclopentadiene (83.9 g, 0.64 mol) and H ₂ PtCl _6.
Heat to a mixture with 6H ₂ O (0.0148 g) (30 ° C.)
Lower tetramethylcyclotetrasiloxane (76.36
g, 0.32 mol). Five minutes after the addition, the reaction mixture exothermed to 193 ° C. The reaction mixture is stirred for 1 hour at 55-70 ° C, transferred to a Teflon-coated mold, and a slight vacuum is applied at 145 ° C for 18 hours.
Cured for hours. This opaque solid plaque is further treated with N ₂
Cured at 285 ° C. in a flashed oven.
The polymers of Examples 7 and 8 were further subjected to mechanical analysis to determine their glass transition temperature (Tg), and storage modulus (G ').
Was measured at various temperatures. The results are shown in the following table.

[0044]

[Table 2] The data in this table shows the relative water insensitivity of the organosilicon polymers of the present invention. Weight gain in boiling water after 5 days is about 0.1%
Met.

Example 9 This example shows that about 58.43% of dicyclopentadiene, 48.
Dicyclopentadiene oligomers consisting of 75% tricyclopentadiene and 5.05% tetracyclopentadiene (analyzed by GC), and tetramethylcyclotetrasiloxane (0.86: 1 carbon-carbon double bond to hydrosilane group 2 shows the production of a novel thermoset polymer according to the invention by reacting (ratio).

[0046] _{H 2 PtCl 6 · 6H 2 O} 0.0076g and dicyclopentadiene oligomer 21.71g (0.1
2 mol) was prepared by heating the two materials to 50 ° C. for 1 hour under a dry nitrogen blanket. To the yellow complex (complex temperature was 71 ° C.) was added tetramethylcyclotetrasiloxane (16.0 g, 0.07 mol). The reaction exothermed to 153 ° C. in 8 seconds. The yellow solution was cooled to 30 ° C., poured into a Teflon-coated slot mold and cured at 150 ° C. for 16 hours and at 200 ° C. for 4 hours. 1.27cm × 7.62cm × 0.32c
m (1/2 "x 3" x 1/8 ") specimens are taken out of the mold and 0.5 hours at 100 ° C, 0.5 hours at 150 ° C, 2 hours at 200 ° C, 2 hours at 225 ° C. Cured for 2 hours at 250 ° C. and 16 hours at 280 ° C. The final polymer is a hard glassy solid, has a glass transition temperature of 250 ° C. and the weight loss by thermogravimetric analysis starts at 500 ° C. Was.

Example 10 This example illustrates the partial reaction of dicyclopentadiene and tetramethylcyclotetrasiloxane (1: 1 ratio of carbon-carbon double bonds to hydrosilane groups) to give a B-staged prepolymer. Figure 4 illustrates the production of a molded article of the novel thermoset polymer according to the present invention in which the B-stage prepolymer is poured into a mold and heated to complete the polymerization. Reaction vessel dry 25 oz charged catalyst _{H 2 PtCl 6 · 6H 2 O} , was sealed. 83.95 g (0. 0 g) under a nitrogen blanket
635 g) of dicyclopentadiene was charged by syringe. Add catalyst and dicyclopentadiene for 90 minutes 6
Heat at 0-70 ° C. to give a yellow solution which is
Cooled to 0 ° C. Tetramethylcyclotetrasiloxane (76.36 g, 0.317 mol) was added and an exothermic reaction started in 2 minutes, eventually reaching 193 ° C. 55 ° C
After cooling the sample to 12.7 cm x 12.7 cm x 0.32 c
m (5 "x 5" x 1/8 ") Teflon lined aluminum molds The polymer was polymerized under a blanket of nitrogen at a temperature in the range of 120-280 ° C. The electrical properties of are shown below:

[0048] A sample of the polymer of Example 10 was immersed in boiling water for 5 days. The sample weight increased by 0.1%. Sample dimensions (6.75,
1.30 cm, 0.32 cm) had no change after boiling water treatment. Modulus / temperature curve and glass transition temperature (250
C) did not change due to the boiling water treatment.

Example 11 This example demonstrates a novel thermal process according to the invention for reacting dicyclopentadiene with methylhydrocyclosiloxane using a carbon-carbon double bond to hydrosilane group ratio of 0.7: 1.
1 illustrates the production of a curable polymer. 237 ml (8.35 g) of chloroplatinic acid (0.0035 g) in a dry box under a nitrogen blanket
Ounce) and sealed in the septum. Dry dicyclopentadiene (8.08 g) was injected into the reaction vessel by hypodermic syringe. The contents of the reaction vessel were heated to 60-65 ° C. for 1 hour under a nitrogen blanket to dissolve the chloroplatinic acid. Dry air was flowed through the reaction vessel for 10-15 minutes and the contents were cooled to 31 ° C. 54% tetramethylcyclotetrasiloxane, 20% pentamethylcyclopentasiloxane, 5% hexamethylcyclohexasiloxane, 19% higher methylhydrocyclosiloxane (up to (CH ₃ (H) SiO—) ₂₀ ); And inject methylhydrocyclosiloxane (11.93 g total) consisting of 2% linear methylhydrosiloxane;
The reaction exothermed to 179 ° C. Reaction product at 60 ° C
And then poured into a Teflon-coated stainless steel mold. Place the mold in a vacuum oven and apply vacuum (approx.
mHg, vacuum pump) for 10-15 minutes.
The mold was then heated at 180 ° C. for 6 hours, 225 ° C. for 6 hours, 235 ° C. for 2 hours and 285 ° C. for 4 hours under nitrogen.
The polymer of this example shows a thermosetting behavior when polymerized at 225 ° C. The polymer has no melting point, but softens at 100 ° C. to a soft, extensible elastomer. The polymer is a tough leathery solid at room temperature. 360 until it splits
有 す る It has enough flexibility to twist.

EXAMPLE 12 This example uses monomers in such an amount that the ratio of carbon-carbon double bonds to hydrosilane groups is 0.85: 1, with final heating at 130 ° C. for 15 hours and 160 hours for 6 hours. 2 shows the preparation of a novel thermoset polymer according to the invention by reacting dicyclopentadiene with methylhydrocyclosiloxane as in Example 11, except at 180 ° C., 180 ° C. for 16 hours, 200 ° C. for 4 hours and 225 ° C. for 4 hours. . The thermoset polymer formed after heating to 225 ° C. was tougher than that obtained from Example 11. This rigid solid polymer retains a high modulus up to 200 ° C. and behaves as an elastic when heated to 235 ° C.

EXAMPLE 13 This example uses monomers in such an amount that the ratio of carbon-carbon double bonds to hydrosilane groups is 1.15: 1, with final heating at 150 ° C. for 4 hours and 235 ° C. for 2 hours. And shows the preparation of a novel thermoset polymer according to the invention by reacting dicyclopentadiene with methylhydrocyclosiloxane as in Example 11, but at 285 ° C. for 4 hours.

Example 14 This example is similar to Example 13 except that the amounts of monomers used were such that the ratio of carbon-carbon double bonds to hydrosilane groups was 1.30: 1. 1 shows the preparation of a novel thermoset polymer according to the invention by reacting with a hydrocyclosiloxane. All of the polymers obtained in Examples 12-14 show thermosetting properties and do not melt or lose their shape below the decomposition point of the polymer (400-500 ° C). Polymers prepared from reactants having a carbon-carbon double bond: hydrosilane equivalent ratio of close to 1: 1 are post-cured at 285-300 ° C., increasing their glass transition temperatures to the range of 260-300 ° C. . The cross-link density of the polymer was high enough to prevent segment migration or network deformation.

EXAMPLE 15 This example uses reactants in amounts such that the ratio of carbon-carbon double bonds to hydrosilane groups is 1.46: 1, with final heating at 150 ° C. for 6 hours and 200 ° C. for 6 hours. 2 hours 23
Figure 7 illustrates the preparation of a novel thermoset polymer according to the invention by reacting dicyclopentadiene with methylhydrocyclosiloxane as in Example 11, except at 5 ° C and 285 ° C for 4 hours. Example 15 shows the polymerization at the transition from thermoset behavior to thermoplastic behavior. When polymerized up to 200 ° C., the sample softened at about 120-125 ° C. to become a highly compressible elastic body. When the sample was post-cured at 285 ° C, the glass transition temperature increased slightly to 200 ° C.
The degree of cross-linking was limited by the available hydrosilane groups.

Example 16 This example is such that the ratio of carbon-carbon double bonds to hydrosilane groups is 1.61: 1 and the final heating is 150 ° C. for 6 hours, 200 ° C. for 6 hours, 235 for 8 hours. 2 shows the preparation of a novel thermoplastic polymer according to the invention by reacting dicyclopentadiene with methylhydrocyclosiloxane as in Example 11, except at 285 ° C. and for 4 hours at 285 ° C.

EXAMPLE 17 This example demonstrates a novel thermoplastic according to the invention in which dicyclopentadiene is reacted with methylhydrocyclosiloxane in such an amount that the ratio of carbon-carbon double bonds to hydrosilane groups is 1.75: 1. 1 shows the production of a polymer. In a nitrogen stream,
0.0953 g of chloroplatinic acid in a sealed 8 oz. Reaction vessel
With 158.8 g of dicyclopentadiene and 1.5 at 70 ° C.
By heating for hours, a catalyst solution containing 600 ppm of chloroplatinic acid was produced. By diluting 30 g of the above catalyst solution with 90 g of dicyclopentadiene,
A 50 ppm chloroplatinic acid solution was prepared. A portion (7.92 g) of the resulting chloroplatinic acid solution was weighed together with 4.59 g of dicyclopentadiene into a 7-inch reaction vessel to give a concentration of 95 ppm of chloroplatinic acid in dicyclopentadiene (0.185 g of olefin). Gram equivalent). Then 7.21 g of methylsiloxane (described in Example 11)
(0.106 hydrosilane equivalents) was injected into a sealed reaction vessel at 23 ° C. When the reaction mixture was heated to 36 ° C., it exothermed slightly and the temperature rose to 60 ° C., at which time the mixture became viscous. The reaction product was degassed by applying a vacuum (15 mmHg) to the contents of the reaction vessel at 45 ° C. for 10 minutes. The product is poured into a Teflon-coated stainless steel mold and placed in a nitrogen blanket for 6 hours at 150 hours.
200 ° C for 20 hours, and 225-235 ° C for 6 hours
Heated. 7.62cm x 1.27cm removed from the mold
The 0.32 cm (3 "x 1/2" x 1/8 ") sample was a clear, hard solid having a melting point of 117-125 ° C. Could not be.

The polymers of Examples 16 and 17 were 225-235
Even when polymerized at <RTIgt; C, </ RTI> it does not form a complete polymer network. They are completely thermoplastic and form viscous, flowable liquids above their melting point. The solid can be ground to a powder. The properties of the prepared polymers of Examples 11 to 17 are shown in the following table.

[0057]

[Table 3]

Example 18 This example illustrates the production of a graphite fiber composite. Chloroplatinic acid (0.0185 g) was weighed into a reaction vessel in a dry box, and the reaction vessel was sealed. Dicyclopentadiene (47.15 g, 0.357 mol, 0.7
14 eq.) And the mixture was heated at 60 ° C. with stirring for 1 hour. After cooling to 36 ° C., tetramethylcyclotetrasiloxane (44.67 g) was injected. The sample exothermed to 192 ° C. in 2 minutes. The product is cooled and 12.7cm x 12.7cm of square woven graphite fiber cloth
12.7 cm x containing 10 (5 "x 5") sheets
Injected into 12.7 cm x 0.32 cm (5 "x 5" x 1/8 ") Teflon lined molds. Load molds in oven under nitrogen blanket for 15 hours at 130 ° C, 6 hours 16 hours.
Heated to 0 ° C and 180 ° C for 12 hours. The resulting composite has good flexural strength (468860 kilopascals (6
8,000 psi)) and had a modulus (32.4 × 10 ⁶ kPa ^{(4.7 × 10 6 psi))} .

Claims (14)

(57) [Claims] 1. The residue of (a) a cyclic polysiloxane and the residue of (b) a cyclic hydrocarbon are completely and alternately completely bonded to a silicon bond via carbon, and the (a) cyclic polysiloxane is represented by the following formula: Formula 1 (Wherein, n is an integer of 3 to 20, R is the same or it may also be different One have Kusoshite each R is hydrogen, substituted or unsubstituted alkyl or alkoxy group of saturated, substituted or non-substituted aromatic or an aryloxy group, any
Of which hydrogen is must at least 2 Tsunison standing silicon atoms in the molecule) In the case, the (b) at least two non-aromatic carbocyclic hydrocarbon group in the ring - carbon double Has a heavy bond and the ratio of the carbon-carbon double bond in (b) to the hydrosilane group in (a) is greater than 0.5: 1 to 1.8: 1 and (a) and (b) A crosslinked organosilicon polymer, characterized in that at least one of the above has more than two reactive sites. 2. The cyclic hydrocarbon residue is a divalent saturated residue based on a cyclic polyene, and includes norbornadiene, dicyclopentadiene, tricyclopentadiene, hexahydronaphthalene, dimethanohexahydronaphthalene, and norbornadiene. Selected from the group consisting of
The organosilicon polymer according to claim 1. 3. The organosilicon polymer according to claim 1, wherein the cyclic hydrocarbon residue is a divalent saturated residue based on norbornadiene. 4. The organosilicon polymer according to claim 1, wherein the residue of the cyclic hydrocarbon is a divalent saturated residue based on dicyclopentadiene. 5. The organosilicon polymer according to claim 1, wherein the silicon-containing residue is a polyvalent residue based on a cyclic polysiloxane or a mixture of cyclic polysiloxanes. 6. A carbon-carbon double bond in the ring of (b) and (a)
The organosilicon polymer according to claim 1, wherein the ratio to the hydrosilane group in the above is more than 0.7: 1 and up to 1.3: 1. 7. A carbon-carbon double bond in the ring of (b) and (a)
In the ratio of from 0.8: 1 to 1.1:
2. The organosilicon polymer of claim 1, wherein the number is up to 1. 8. (a) residues of tetrahedral siloxysilane and the residue of the (b) cyclic hydrocarbon is a silicon-bonded via a carbon
Alternately bonded completely, the (a) tetrahedral siloxysilanes are embedded image (In the formula, R is good even though different from one identical or Kusoshite it
Each of R is hydrogen, substituted or unsubstituted alkyl or alkoxy group of saturated, substituted or unsubstituted aromatic or aryloxy radical, a hydrogen least two silicon atoms in the molecular in either case It shall exist
A have), the (b) at least two non-aromatic carbocyclic hydrocarbon group in the ring - and carbon double bond (b)
The ratio of the carbon-carbon double bond at to the hydrosilane group at (a) is greater than 0.5: 1 to 1.8: 1 and at least one of (a) and (b) is greater than 2 A crosslinked organosilicon polymer having a large number of reactive sites. 9. The cyclic hydrocarbon residue is a divalent saturated residue based on a cyclic polyene, and includes norbornadiene, dicyclopentadiene, tricyclopentadiene, hexahydronaphthalene, dimethanohexahydronaphthalene and norbornadiene. Selected from the group consisting of
An organic silicon polymer according to claim 8. 10. The organosilicon polymer according to claim 8, wherein the cyclic hydrocarbon residue is a divalent saturated residue based on norbornadiene. 11. The organosilicon polymer according to claim 8, wherein the residue of the cyclic hydrocarbon is a divalent saturated residue based on dicyclopentadiene. 12. The organosilicon polymer according to claim 8, wherein the silicon-containing residue is a polyvalent residue based on tetrahedral siloxysilane or a mixture of tetrahedral siloxysilanes. 13. A carbon-carbon double bond in the ring of (b)
9. The organosilicon polymer according to claim 8, wherein the ratio to the hydrosilane group in (a) is greater than 0.7: 1 and up to 1.3: 1. 14. A carbon-carbon double bond in the ring of (b)
The ratio to the hydrosilane group in (a) is from 0.8: 1 to 1.
9. The organosilicon polymer of claim 8, wherein the ratio is up to 1: 1.