JPS5939897A - Organocsilicon compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I [R<1> is 1-6C monofunctional hydrocarbon; R<2> is 1-4C bifunctional hydrocarbon; Z is group shown by the formula II (R<3> and R<4> are 1-6C monofunctional hydrocarbon; a is 1, 2, or 3), group shown by the formula III (R<5> is 1-6C monofunctional hydrocarbon; R<6> is 1-6C monofunctional hydrocarbon, or trimethylsiloxy)]. EXAMPLE:A compound shown by the formula IV. USE:A surface improver of room-temperature curing organopolysiloxane. Making the surface of cured material hydrophilic, and applicable and preventing dirt from attaching it. PROCESS:For example, a guanidine derivative (e.g., tetramethyl-guanidine, etc.) shown by the formula V is reacted in a solvent such as toluene, etc. with a halogenated organosilicon compound [e.g., 3-chloropropylbis(trimethylsiloxy) methylsilane, etc.] shown by the formula X-R<2>-Z(X is halogen) which is dropped, under heating, to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention seeks to provide novel organosilicon compounds.

That is, the present invention is based on the general formula %formula%( It relates to an organosilicon compound represented by

In the above formula (:), R is the same or different group selected from monovalent hydrocarbon groups having 1 to e carbon atoms, R is a divalent hydrocarbon group having 1 to 4 carbon atoms, and 2 is the formula It is a group selected from organonyl groups represented by

The above formula +17 or (Machinaka, R, R and R are the same or different groups selected from monovalent hydrocarbon groups having 1 to 6 carbon atoms, R6 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and the same or different groups selected from trihydrorubylsiloxy groups; a is 1.2 or 3;

Specifically, the monovalent hydrocarbon group having 1 to 6 carbon atoms represented by R1, R3, R4, R11, and R6 includes an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, or Cycloalkyl groups such as cyclopentyl groups, alkenyl groups such as vinyl groups or allyl groups, aryl groups such as phenyl groups or quinryl groups, aralkyl groups, or the hydrogen atoms of these groups are partially substituted with halogen atoms, etc. The base t can be given.

Furthermore, the divalent hydrocarbon group having 1 to 4 carbon atoms represented by R includes a methylene group and an ethylene group.

Pro, lene groups, imbutylene groups, etc. can be mentioned.

Specific examples of the novel organosilicon compound of the present invention are shown below. However, in the following description, Me is 0H3-1Pr is 0
3H, -1Ph indicates C, vi, OH, =OH-'r.

(Me, N-)20=N-Oa-8iMa.

(Mo2N-), 0-N-CH20-N-CH2-8I
N-)20=N-OH2-8i (Me), -P
h(Mo2N-), 0=N-OH,-8i (Me
), I”Vi(Mo2N-)20=N-03H,-81
-0-81Me 8, Me Me (M13.N-), l0=N-0,H, -81(-0
-81Mes) 2, the organosilicon compound according to the present invention can be roughly divided into two methods, and the first method is, for example, the formula % formula % (1) (where R has the same meaning as above) A guanidine derivative represented by the formula An example of a method is to mix the ingredients in a slurry formulation system and then react for 5 to 30 hours while heating.

The reaction molar ratio (+1)/+11 of the above guanidine derivative (1) and the halogenated organosilicon compound (wheat) is preferably 2 or more, preferably 2.5 to 3.5, and the reaction temperature is 50 It is desirable that the temperature is in the range of ~150°C.

The reaction can also be carried out in the presence of a solvent, and examples of the solvent that can be used here include toluene, xylene, benzene and hechitin.

In addition, as another synthesis method, 1, for example, an allyl group-containing guanidine derivative represented by the formula % formula % (where R1 has the same meaning as above) and the formula % formula % (1) (where 2 has the same meaning as above) meaning)〉5i
A method of carrying out an addition reaction with an -H bond-containing organosilicon compound in the presence of a suitable catalyst can be mentioned.

The above guanidine derivative tllllj and the organosilicon compound (
The molar ratio of the guanidine derivative to the organosilicon compound is preferably equal to or more than 1.2 times the mole of the guanidine derivative, preferably 1.2 times or more, and the reaction temperature is 26 to 200°C.
The temperature is preferably in the range of 50 to 150°C.

As a reaction catalyst that can be used in carrying out this reaction, for example, a complex compound of a metal element belonging to Group VI of the periodic table can be used. Examples include chloroplatinic acid, alcohol-modified chloroplatinic acid (see U.S. Pat. No. 3,220,972), and complexes of chloroplatinic acid and olefins (U.S. Pat. No. 3,159,601, U.S. Pat. 159
．． 662 or 3.77 to the specification of 452), solid platinum completely supported on a carrier such as platinum black, alumina, or silica, and rhodium-olefin complexes. solvents, ketone solvents, ether solvents.

It is preferable to use it after dissolving it in a hydrocarbon solvent or the like.

Note that benzene is also used in this Ct> reaction.

Any suitable solvent such as toluene, xylene or hechitin may be used.

The organosilicon compound of the present invention can be applied to various uses.1 For example, when it is added to conventionally known room temperature curing organopolysilochitin, its surface properties can be improved, and in particular, it has water repellency. For room temperature curing organopolysiloxane, the surface of the cured product obtained from this!
The surface of the cured product can be made hydrophilic! It is possible to store it and prevent dirt from attaching to it.

In addition, room-temperature curing organopolysilochitin is widely used as a sealing material for construction, and in recent years its demand has increased as a sealing material for high-rise buildings.On the other hand, the use of silicone sealing materials for marble, glass, aluminum sash, etc. However, by adding the organosilicon compound according to the present invention to them in an appropriate manner, staining can be significantly prevented.

Furthermore, the silicon compound of the present invention is a curing catalyst (deacetone type) that cures by releasing acetone even among organovorin lokitins that cure at room temperature (cross ffR agent).
It shows an extremely excellent effect.

Note that these are typical application examples of the organosiliconized metal according to the present invention, and the present invention is not limited to these.

Next, examples of the present invention will be given.

Example 1 103.8 g of tetramethylguanidine and 6 g of toluene
9.2. A PY reflux condenser, a stirring rod 1 dropping funnel, and a four-bottle flask with an internal volume of 500 cm were equipped with a temperature #t, and the temperature was maintained at 1130' ccm.
After the dropwise addition, which took 1 hour, was heated and stirred at 130°C for 14 hours, the salt produced was removed by filtration, and the F-tatsu was distilled under reduced pressure.
Refractive index is 1.4420 at 124℃72 HI (25℃)
A fraction of 51.2N having physical properties was obtained. Does this compound correspond to the following molecular formula based on IR, NMR, Go-M8, and elemental analysis? confirmed.

Me (Me, N-), O"N-0, H, -Si (-0S
iMe, )2o IRlNMR, IGo-Mk3 analysis value* 0HOI3 Internal standard (same below) calculated value
47.7 10.4 22.3 Analysis value 4
7.9 10,1 22.2 Example 2゜Tetramethylguanidine 103.7. P and toluene 69.21i with a reflux condenser, a stirring rod, a dropping funnel and a temperature needle were charged into a four-piece flask with contents FiI50QIIj, the temperature t was maintained at 130°C, and 3-chloropropyltrimethylsiloxydimethylsilane 67.5.
It took 11v of P'PI to drip. After finishing dropping, 13
When the IP solution was heated and stirred at 0°C for 14*1 iJj, and then the salt produced was removed by filtration and distilled under reduced pressure, the boiling point decreased to 102/2 IJ.

51.4.9 fractions having physical properties of refractive index power 1.4494 (25° C.) were obtained. This compound has rR, NMR
.

() It was confirmed from O-MS and elemental analysis that it corresponds to the following molecular formula (=).

Me (Me, N--0-N-0, H6-81-0-81M
e.

e o IR, NMR, Go-MS analysis value calculation value 51.4 11.0 18.5 analysis value
51,7 10.8 18.4 Example 3゜Tetramethylguanidine 101.2.9 and toluene 67.81IY were charged into a four-bottle flask with an internal volume of 50011IJ equipped with a reflux condenser, a stirring rod, a dropping funnel and a thermometer, Maintain temperature g130℃ζ2, 3-chloropropyltrimethylsilane 45.2I! v1 battleriIJ
It took a while to drip. After the dropwise addition was completed, the mixture was heated and stirred at 130°C for 8 hours, and the salt formed was removed using filtration.
f'aw When distilled under reduced pressure, the boiling point was 97-98℃ 74
The fraction HII has a refractive index of 1.4625 (25°C) and a physical property of 44.5. P was obtained. This compound has an IR
, NMR, Go-MS and elemental analysis, it was confirmed that it corresponded to the following molecular formula.

(Me, N-)20=N-011H, -81Me.

o IRlNMR, GO-MS analysis value 0 (%)
H (%) Sl (%) Calculated value 57.6 11.9 12.2 Analytical value 57.7 11.8 12.0 Example 4゜Tetramethylguanidine 103.0.9 and toluene 77.0 Refluxing N The mixture was placed in a four-tube flask with an internal volume of 5,001 cm equipped with a condenser, a stirring funnel, a dropping funnel, and a thermometer, and the temperature was maintained at 90° C., and 36° 81 I of chloromethyltrimethylsilane was added dropwise over 1 hour.

After the dropwise addition was completed, the mixture was heated and stirred at 90°C for 24 hours, and then the formed salt was removed by filtration, and fPgY was distilled under reduced pressure. The boiling point was 65-67°C, 15 Hg, and the refractive index was 1.4.
30.5 g of a fraction having physical properties of 60 (at 25° C.) was obtained. It was confirmed from IR, NMR, C)O-MS and elemental analysis that this compound corresponds to the following molecular formula (2).

(MeN-)O=N-OH-8iMe.

2 2 2 o IRlNMR, GO-MS8 analysis value (%) H (%) to si) H1 calculated value
53.7 11.5 13.9 Analysis value 53
．． 6 11.3 13.7゜Example 5゜Tetramethylguanidine 103.211 and toluene 67.2. A FY reflux condenser, a stir bar, a dropping F funnel, and a temperature #' were placed in a 5001 four-tube flask, and the temperature was maintained at viao°C.

Glorometerphenyldimethylsilane 55.4#'21
It dripped in time. When the dropwise addition was completed at 7%, the mixture was heated and stirred at 130°C for 7 hours.
When the liquid was distilled under reduced pressure, 65.4 # of fractions with physical properties and a boiling point of 126-b was obtained. This compound was confirmed to correspond to the following molecular formula from IR, NMR, Go-MS and elemental analysis.

e (MθN-)O=N-OH-8i-Ph2 1 e OIR, NMR and Go-M88 analysis values Elemental analysis value 0 (%) H (%) Sl (%) Calculated value 63.8 9.6 10. 7 analysis value
63.6 9.3 10.8 Example 6゜Tetramethylguanidine 103.6p and toluene 6
9.311' Pour into a 500 d four-bottle flask equipped with a reflux condenser, a stirring rod, a dropping funnel, and a thermometer, maintain the temperature vloO'cc, and run 40.4.9 i of chloromethylvinyldimethyl for 1 hour. dripped. After the completion of droplet F, the mixture was stirred at 100℃ for 24 hours, and the salts formed were removed by filtration, and the P solution was distilled under reduced pressure. 32 fractions with physical properties of
．． 6.9 was obtained.

It was confirmed from IR, NMR, Go-MS and elemental analysis that this compound corresponds to the following molecular formula.

e o IR%NMR and Go-M88 analysis value Original analysis value 0 (%) H (%) Sl (%) Calculated value 56.3 10.9 13.2 Analysis value 5
6.6 10.7 13.1 Example 7゜1,i, 3.3.5.5.7-Hebutamethylcyclotetrasilochitin 296.7# and platinum-octanol complex 2g of 2% octatool solution H Internal volume 500 with far flow cooler, stirring rod 1 dropping funnel and thermometer
1. Preparation of 2 Yotsuro flasks C.

Allyltetramethylguanidine was added dropwise over a period of 155.2 JFY while maintaining the temperature at -100 to 110°C. After completion of the dropwise addition, heat and stir at 100 to 110°C for 30 minutes, then cool to 50°C, and add benzothiazole 2. S'Y was approved. When this reaction mixture was distilled under reduced pressure, 332.7Ii of a fraction having physical properties with a boiling point of 148-b was obtained. It was confirmed from IR, NMR, Go-MS and elemental analysis that this compound corresponds to the following molecular formula.

o IRlNMR and Go-M8 analysis value 0 Elemental analysis value O (%) H (%) 81 (%) Calculated value 41.1 9.0 25.7 Analysis value
41.3 8.7 25.4 Example 8゜1,3.5.7-titramethyl-1.3.5-)di-n
-Propylcyclotetrasiloxane 384.39 and platinum-octanol complex 2% octatool solution 2.0
．． 1 - Charge allyltetramethylguanidine to a 1fIII four-bottle flask equipped with a reflux condenser, stir bar, addition funnel and thermometer, maintaining the temperature at 100°C, and add allyltetramethylguanidine 155. The dropwise addition took 21 hours. After dropping, heat and stir at 100℃ for 30 minutes, then 50℃.
2 g of benzothiazole was added dropwise.

When this reaction mixture was distilled under reduced pressure, the boiling point was 143~
145°C 70.8mm HE, refractive index 1.449 (25°C
) reaction product is 536. OII was obtained. This compound was confirmed to have the following molecular formula from IRlNMR, Go-MS, and elemental analysis.
R, NMRlGo-M8 analysis value 0 element Cumulative analysis value 0 (%) H (%) Sl (%) Calculated value 48.3 9.8 21.5 Analysis value
48.5 9', 8 21.7 Example 9゜1. 3. 5.7-Titramethyl-1. 3.5-tris(trimethylsiloxy)cyclotetrasiloxitin 5
05.3.9 and platinum-octanol complex 2% octatool solution fi2.0.9 were charged into a four-way flask with an internal volume of I equipped with a reflux condenser, a stirring rod, a dropping funnel, and a thermometer, and the temperature was adjusted to 100 degrees. The temperature was maintained at 0.degree. C., and allyltetramethylguanidine 155.3.9 was added dropwise over a period of 1 hour. After finishing the dripping process, heat and stir at 100℃ for 30 minutes.
Then, it was cooled to 50°C, and benzothiazole 2.
Dropped 9Y.

When this reaction mixture was distilled under reduced pressure, the boiling point was 146-
148℃/0.8 mxH7/, refractive index 1.442
A fraction of 526.3N having physical properties (at 25°C) was obtained. This compound was confirmed to correspond to the following molecular formula from IR, NMR, Go-MS, and elemental analysis.

o IR, NMR and Go-MS analysis values ° Elemental analysis
C (%) H (%) Sl (%) Calculated value 37
．． 1 8.9 30.3 Analysis value 37.3
8.9 30.6 Procedural Amendment June 15, 1980 Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office■, Minor Case Indication 1988 Patent lI'! No. 149007 2, Name of the invention Organosilicon compound 3, Relationship to the case of the person making the amendment Applicant's name (206) Shin-Etsu Chemical Co., Ltd. 4, Agent 1) Specification page 11, 5- [Curing catalyst (crosslinking agent NYrl+1! chemical cocatalyst)” and cocatalyst in line 6.

2) Correct the following in the second line of the table on page 17 of the specification.

3) The face plate on page 19 of the specification shall be amended as follows.

-1+” 4) Correct the chemical formula next to line 7 on page 20 of the specification as shown below.

r Me (Me N-) 0=N-OH-81-Ph22
21 Y8'' 5) Correct the chemical formula on page 22, line 1 of the specification as follows.

[Me ■ (Me N-) 0=N-OH-8i -Vi2
2 2 Me3” 6) Change the front metal body on page 22 of the specification as follows (
Make two corrections.

7) The face metal on page 24 of the specification shall be amended as follows.

8) The face plate on page 26 of the specification shall be amended as follows.

9) The cover plate on page 28 of the details is as follows≦
Make two corrections.

[

Claims (1)

[Claims] 1. General formula % Formula % 2. All R1's in the general formula are 0H1-, and W is 0
A group selected from H-1+OH+ or 223-0H-OH-OH-, and 1
3 OH3 2 is -8iR or (where R3 is a group selected from 0H3-1OH, =OH- or α, R6 is selected from OH1-1OH-, OH- or (OH3), 8i0-1111 1
7. The organosilicon compound according to claim 1, which is a nryl group represented by the following formula.