JPS61174224A - Polymer having hydrolyzable group on each terminal and its production - Google Patents

Abstract

PURPOSE:To produce the titled polymer useful as a sealant, an adhesive or the like, by reacting a specified SH group-containing polymer with an organosilane. CONSTITUTION:A polyolefin polyol, MW of 1,000-5,000, of formula I (wherein m is 50-400) is mixed with a mercaptoalkanoic acid of formula II (wherein R<1> is a 1-6C bivalent hydrocarbon) and a dicarboxylic acid of formula III (wherein R<2> is a 1-12C bivalent hydrocarbon or a thioether bond-containing 4C or lower bivalent organic group) at a OH/COOH stoichiometric molar ratio of 0.8-1.2. This mixture is subjected to a dehydration reaction at 50-250 deg.C in the presence of an acidic esterification catalyst (e.g., sulfuric acid) to obtain a SH group-containing polymer of formula IV (wherein l is 0-20 and k is 0 or 1). This polymer is reacted with an organosilane of formula V (wherein R<3> is a 1-6C monovalent hydrocarbon group, R<4> is a 2-8C bivalent hydrocarbon group or a 4-8C ester bond-containing bivalent hydrocarbon group, X is a hydrolyzable group and a is 0-2) at 40-120 deg.C in the presence of a sensitizer, a peroxide, etc., to obtain a polymer having a hydrolyzable group of formula VI on both terminals.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention is directed to novel polymers that have not yet been published in literature, particularly to sealants, adhesives, coating materials, etc., which become crosslinked polymers through hydrolytic condensation. 9. (Structure of the Invention) The present invention relates to a polymer having 5 dihydrolyzable groups at both ends and 70) a manufacturing method useful as a sealant, an adhesive, and a coating material. This relates to a polymer having a dihydrolyzable group, which also has the general formula %(11) where R' is a divalent hydrocarbon group having 1 to 6 carbon atoms, R
2 is a divalent hydrocarbon group having 1 to 12 carbon atoms (1) or a divalent organic group having 4 or less carbon atoms containing a thioether bond, R1 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R4 is a monovalent hydrocarbon group having 2 carbon atoms. ~8
Q] A divalent hydrocarbon group or a divalent hydrocarbon group containing an ester bond having 4 to 8 carbon atoms, X is a hydrolyzable group, a is (),
1 or 2, m is 50-400, l is 0-20, k is 0
Or as shown in 1).

The carbon number 1 to 6 Q) divalent hydrocarbon group represented by R1 is -OH, -1-〇□H4-1-0, H6-1OH
.

Groups such as -0H-1-0,H,- or divalent hydrocarbon groups having 1 to 12 carbon atoms represented by R include -OH,7, -0, H4-, -0,H,' -1-C), Hl, -1-O
, H4-1'11H16% cl. H2゜-1'12
[Q] groups such as H114-, divalent organic groups with 4 or less carbon atoms containing a thioether bond, 10H2-8-OH2-
1-〇□H4-8-02H4-1 Monovalent hydrocarbon groups having 1 to 6 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, vinyl group, allyl group, etc. Examples include alkenyl groups and aryl groups such as phenyl groups. In addition, the number of carbon atoms represented by R4 in this formula is 2-
The divalent hydrocarbon of 8 is 10H2-1-0□H4-2
Groups such as O, Ha-1-OH2-OH, -0, H, - are mono'OH-0H-0000H-2-0H as divalent hydrocarbons containing an ester bond with 4 to 8 carbon atoms (7). -0)
(-0000H-1m6.,,j,",'j,
1-OH-OH-0000H-1-0H, -OH,70
Examples include groups such as 000H,-, but this a-m-t
-k is a positive number of I) mentioned above, and IJ,
This general formula (shown above) is a polymer having a hydrolyzable group Y at both terminals.
) 11,00000. H4S-10□H4(CH2)
□6゜0000□h4so□)I4Coo(OH2)1
60-OH3-oaoa, b, 80. H45i(OOH3)2-OH
3 (OH30)38103H60000H-OH2B02
H,C00(OH2'),. -OH.

■ 10OOO2H4soa2- am4ooo, H65i
(ocH3)3-OE.

(OH30)3E11Qll)i60000HOH2S
02H4000(OH2)□, --00002H4So
□H,000(OH2)0.0000. , H,5OH
2-OH3 10f-100003H6Si(OC!H3)3-OH
3- (OH30H20)2810□H480,H,000(
OH,,l,' 6ao -OR.

-OH80) 181 (OOOHH).

H3 ■ (OH30H20), 810. H45oH2000(O
H2) 161)000-- C2H,000(OH2)
1600000H2802H4-OH3 ■ -81(OOH20B, )2+ 0)]3 ■ (OH30), SiO□H, oH, ooo(oH, J,
0oaoo6H4oo〇-OH3-(OH,)1. oO000H2So,H,81(OO
Examples include H, )2, but the above alkoxy groups at both ends may be replaced by methyl ethyl ketoxime group-isobropenoxy group, N-ethylamide group, dimethylamino group rx, etc.

A polymer having hydrolyzable groups at both ends represented by the above general formula (1) can be produced using a polyolefin polyol represented by the general formula % (2) (where m is the same as above) as a raw material. The hydroxyl groups at both ends of this product are reacted with mercaptoalkanoic acid represented by the general formula % (3) (where R1 is the same as above), or the above polyolefin polyol is reacted with the general formula % in advance. % (4) (where R2 is the same as above) is reacted to extend the chain, and then the above mercaptoalkane #! are reacted to synthesize a polymer in which both ends are blocked with SR groups and represented by the general formula % (6) (herein, RB, R', It can be obtained by reacting an organosilane represented by (X is the same as above).

The polyolefin polyol represented by the general formula (2) is a polymer with a molecular weight of 1,000 to 5,000, which has a saturated hydrocarbon skeleton and is blocked at both ends with hydroxyl groups.13. This includes liquids at room temperature to waxy solids with melting points of 75°C or higher.
[Both are Mitsubishi Chemical Industries, Ltd. product names]
These physical properties are published as follows.

Furthermore, examples of the mercaptoalkanoic acid represented by the general formula (3) above include mercaptoacetic acid-2 to mercaptopropionic acid-α-mercaptopropionic acid-thiosalicylic acid, and dicarboxylic acids represented by the above general formula (4). Examples include aliphatic and dicarboxylic acids such as oxalic acid, malonic acid, succinic acid-glutaric acid, adipic acid, pimelic acid-suberic acid, azelaic acid, sebacic acid-undecaniic acid, dodecanoic acid-brassillic acid-tetradecanonic acid.

Aromatic dicarboxylic acids such as 0-phthalic acid-isophthalic acid and terephthalic acid-β, β′-thiodipropionic acid,
Thiodiacetic acid-α, α′-thiodipropion 11127x
Examples include:

The reaction between the polyolefin polyol represented by the above general formula (2) and the mercaptoalkanoic acid represented by the general formula (3) is carried out at a stoichiometric molar ratio of -9H/-000I (0.8 to 1.2). Mix at a blending ratio within the range of 50
The reaction may be carried out in a temperature range of -250°C. This reaction is preferably carried out in the coexistence of an rxe esterification catalyst such as paratoluenesulfonic acid, benzenesulfone-sulfuric acid, or trifluoroacetic acid, but in order to carry out this reaction easily and uniformly, In addition, in order to remove the produced water from the system, this is preferably carried out in a solvent such as toluene-benzene or xylene-cyclohexane. Note that this reaction can be carried out at normal pressure. ．．
ヮ-t-Okay, yooooo 1. □1. Well-known techniques for nitrification techniques such as TSO may also be used.

The product obtained by this reaction (1) has the above-mentioned general formula (5
) is a polymer whose both ends are blocked with 8H groups, but the organosilicon polymer of the present invention represented by the above general formula (1) is a polymer represented by this general formula (5). The organosilane represented by the general formula (6) can be obtained by reacting the organosilane represented by the general formula (6) with the formula OH,=0')ISi(O
OI(,)3゜0)12=OR-8i (00)13
No2-OB.

0H2=OH-OH2Si(OOH3),.

OH,=OH−OR2Si(QC)H,), +0B2
:0)10. H,81(OOH,),,.

0H2=OHO6H, 5i(OOH3)2°OH.

Oh.

0H2=O)406H40H2NHO3H681(00
□Hs), -OH3 C) I2=O) 106H40H2Nf-103H681
(00□H1l)2-OH2=OH(16)]40H2
NHO2H4NHOBH6Si -0H2=OH06H
4NHO□H4NHO3H681 (OCIH,) 2-0
H2=OHO,H,OH2'NHOH28i(OOH3
)3 +0H2-0-00003H681(OCIH3
), -0]-12=0-0000. H681 (OOH3
), -0E2=O-0000H,5i(OOH3),'
+OH,=OR-(30003H,81(OOH,)8
゜υ3 0H2=CIl)l-00003H6Si(00)13
)2.

OH=OFl-0000H281(OOH3), -0H
=CIH-OH2N]'103H681 (002H,)
, -0H=OH-OR2NH02H481(OOH
3).

0H=OH'-0H2NHOH281(OOH3)sr
x indicates an alkoxysilane having an unsaturated group and a hydrolyzable group thereof; 1000H;

! A silane compound in which a group such as 1 is substituted or this hydrolyzable group is replaced with a group such as 2
Examples include silane compounds with different groups of seeds or three glazes.

The reaction between the SH group-containing polymer represented by the general formula (5) and the organosilane represented by the general formula (6) may be carried out using a well-known reaction between an SH group and an unsaturated group.

Therefore, is this an addition reaction by ultraviolet irradiation - Radical addition reaction using peroxide 1 Addition reaction catalyzed by a strong base? T is fine. This reaction by ultraviolet irradiation uses an ultraviolet generator such as a high-pressure mercury lamp to produce benzylbenzophenone-Michael's ketone-2-chlorothioxanthone, 2゜4-diethylthioxanthone-benzoin ethyl ether, jetoxyacetophenone, benzyl dimethyl ketal, The reaction may be carried out in the presence of a known sensitizer such as 2-hydroxy-2-methylprobiophenone-1-hydroxycyclohexylphenyl ketone.The addition reaction with monoperoxide can be performed using t-butyl hydroperoxide, di-1-butyl Peroxide - in the presence of a peroxide such as benzoyl peroxide, cumene hydroperoxide, acetyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide - methyl ethyl ketone peroxide, or azobisisobutyronitrile, etc. The reaction may be carried out at 120°C. Examples of the strong base catalyst include silicone compounds such as tetramethylguanidine and guani-1,8-diazo-bicyclo(5,4,0)undecene-7, which are heated at 20 to 200°C. The reaction may be carried out at a preferable temperature. Note that all of these reactions may be carried out in the presence of a solvent, such as benzene-toluene-xylene-hegisan.

Examples include cyclohexane-methylethylketone-dimethylformamide.

One of the polymers of the present invention, which is advantageous in the above-mentioned method, has both ends blocked with hydrolyzable groups, and since this polymer becomes a crosslinked polymer through hydrolytic condensation, light silica is added to it. A composition containing a filler such as Shenzhen Silica calcium carbonate and carbon black, a plasticizer, an adhesion promoter such as a silane coupling agent, and a curing catalyst such as an organotin compound, a titanium compound, and an amine compound has room temperature curability. As shown, this is a sealant and adhesive.
It is considered useful as a coating material.

Next, give reference examples and working examples of the present invention.

Reference Example 1 227g-β of polyolefin polyol polytail HA (previous molecular weight 2.270) was placed in a 1t reaction flask equipped with a condenser-ester adapter and a thermometer.
-Mercagtobropionic acid 22L) Toluene 250.
! ? Then, 1 g of para-toluenesulfonic acid was added, the mixture was stirred, and the mixture was allowed to react at the reflux temperature of toluene, resulting in water! The reaction was carried out for 3 hours while being removed from the thread using an ester adapter, and the reaction was completed with 3.6 g of water produced.

Next, the temperature of the reaction system was lowered to 50 to 60°C, and 5 g of sodium monocarbonate was added to neutralize the p-toluenesulfonic acid.
When toluene was distilled off under conditions of 120°C/20 Hg, a viscous liquid with a viscosity of 155 Boers (at 25°C), a refractive index of 1.4791 (at 25°C), and a specific gravity of 0.888 was obtained. 240 g was obtained, and it was determined that this product had a terminal SR group content of 0.082 mol/100 g, and was represented by the formula %.

Reference Example 2 Polyolefin polyol Polytail HA (described above) 22 was placed in the same 1 t reaction flask as used in Reference Example 1.
9 g of 7L thiodipropionic acid.

250 g of toluene and 19 p-toluene sulfonic acid were added, the temperature was raised with stirring, and the reaction was carried out at the toluene reflux temperature. The water produced was removed from the system using an ester adapter and the reaction was carried out for 3 hours. 8g, so add 11g of β-mercaptopropionic acid.
When the reaction was continued for another 3 hours, the production of water increased by 3.
．． The reaction was completed when the weight reached 6 g.

Then, the temperature of the reaction system was lowered to 50 to 60°C, 5 g of soda carbonate was added to neutralize the para-toluenesulfonic acid, and then
When toluene was distilled off under the conditions of 20°C/20 mmHH, the viscosity was 1,350 Boers (25°C).
) - refractive index is 1.4797 (25°C), specific gravity is 0889
238 g of viscous liquid was obtained hh - this is its terminal S
Since the H base was fixed at 0.040 mol/100g, it was determined that it was expressed as a formula % formula %.

Reference Example 3 Polyolefin polyol polytail HA (described above) 34 was placed in the same 1 t reaction flask as used in Reference Example 1.
01 thiodipropionic acid 181) toluene 350,9
and para-toluenesulfonic acid 2I, heated while stirring, and reacted at toluene reflux temperature for 3 hours while removing the generated water from the system with an ester adapter. 1.8 g of water was generated. Therefore, 11 g of β-mercaptopropionic acid was added to the mixture and reacted for 3 hours, and the reaction was completed with 3.6 g of monohydrogen produced.

Then, the temperature of the reaction system was lowered to 50-60°C, 10g of sodium carbonate was added to neutralize the para-toluenesulfonic acid, and the toluene was distilled off under conditions of 20°C/20nHg through a sieve. The viscosity is 6.300 Bores (25
℃) - 355 g of a viscous liquid with a refractive index of 1.4800 and a specific electric charge of 01890 were obtained.

This product's final @isH group amount is 0.027 mol/10
Since the amount was determined to be 0g, it was determined that the amount was expressed in % formula %.

Example 1 In a 1 t reaction flask equipped with a condenser and a thermometer,
The average composition obtained in Diameter Example 1 is B502H4000(OH,)16o00002H4S
A polymer 245y having 8H groups at both ends represented by H,
29 g of organosilane of the formula OH3 ■ 0H2=OH8i (OOH3), 2 g of azobisisobutyronitrile and 245 g of toluene. ! i'7a' was prepared, the temperature was raised to 80°C while stirring, and the reaction was allowed to proceed for 6 hours.The above organosilane was detected using a gas chromatograph.Since this was not detected, it was determined that the reaction had completed. Then, when toluene was distilled off under the conditions of 120° C./110 ml, 260 g of a viscous liquid was obtained.

This liquid has a viscosity of 420 Boers and a refractive index of 1.4785.
(25℃), specific gravity 0.890, alkoxy group content 0
．． It was determined to be 146 mol/10 (l).

Elemental analysis value is % of theoretical value 77.82 1304 4.72 2.36
2.06 4.57 Analysis value (to) 77, '17 13
．． 17 4,70 2.32 2,04 4.53 and 11. The first chart of this item is an infrared spectrophotometer.
Because the one shown in the figure is +1.

The following formula %formula%) It was confirmed that the

Example 2 A 1 ton reaction flask similar to that used in the example was charged with the uniform composition obtained in Reference Example 2))i80□)]4000
(OH2)16o00002H4B02H4--000
(OH2), 6o Polymer having SH groups at both ends represented by 00002H48H 2440H2-OH8i
15 g of organosilane represented by (0OH3)2,
2 g of benzophenone and 244 ml of toluene were prepared, and while stirring, irradiated with ultraviolet light using an external ultraviolet lamp and allowed to react for 6 hours. When the above organosilane was detected using a gas chromatograph, it was not detected, indicating that there was no reaction. When the toluene was distilled off under the conditions of 120°C/10 Hg, 255 g of a viscous liquid was obtained.
was gotten.

This liquid has a viscosity of 2,200 Boers and a refractive index of 1.4.
800 (25℃), the specific gravity is 0.892, and the total alkoxy group content is determined to be 0.078 morph 100g - this elemental analysis value is the theoretical value (%) 80.02 13.28 3.74
1.87 1.09 2.49 Analysis value (%) 80.
06 13.30 3,71 1.85 1.08 2
．． 42 and 2 Since the chart of this infrared spectrophotometer is shown in Figure 2, the linear formula OH3 (OH8O)2SiO□H,802H4Coo(OH2
)160--00002H4So□H4000(OR2
), 60000-OH.

10□H45o2H481 (OOH3), it was determined that it could not be indicated by I.

Example 3 A 1 ton reaction flask, the same as that used in Example 1, was filled with an average composition of 180□H4'00 in Reference Example 3.
0(OH2), 6o00002)14So2H4--0
00(OH2)16o00002H4802E4COO
--(OH2)1600000□Electrocombinant 1839 with both terminal KSH groups represented by H48H, organosilane represented by the formula OH3 0B2=0)3Si(0OH8)2 7g-Azobisisobutyronitrile 1.5I
and toluene 200,! It was determined that it was as indicated by ilY preparation and stirring.

After raising the temperature to 80℃ and reacting for 8 hours,
When the organosilane was detected using a gas chromatograph, it was not detected, so it was determined that the reaction had finished.Then, the toluene was distilled off under conditions of 120°C, 710mmHg, and 189g of a viscous liquid was obtained. It was done.

This liquid has a viscosity of 6,300 Boers and a refractive index of 1.4
802 (25°C) - The specific gravity is 0.892 and the alkoxy group content is determined to be 0.053 morph 100g - The elemental analysis value is the theoretical value (%) 80.81 13.3.7 3,39
1.69 0.74 1.64 Analysis value (%) 80.8
0 13.40 3,40 1.68 0,72 1.
64, and since the infrared spectroscopy chart of this item is as shown in Figure 3, the following formula % Formula % Refractive index is 1.4790 (25°C) - Specific gravity is 0.895 11 actual examples 4 W Ren 4! /l! Reference Example 1'r: 245 g of the obtained electroconjugate having -i groups at both ends [8] was placed in a 1 t reaction flask similar to that used in 11.

OH3 formula aH2=00000. H65i ((JOH,),
50 g of organosilane represented by - 3 g of organosilicone catalyst represented by and 3 g of toluene
After 3 hours of reaction at 50°C, the presence of the organosilane was detected using a gas chromatograph, and it was determined that the reaction had been completed. After distilling off, 290 g of monoviscous rx liquid was obtained.

This liquid has a viscosity of 350 Boes (25°C) and an alkoxy group content of 0.20 mol/100g, and the elemental analysis values are 75.84 12.60 7.58 2,1
0 1.88 6.25, and the infrared spectroscopy chart of this item is shown in Figure 4 (I), so it is a linear formula OH.

(0H30)11 S 103 H60000HOH2
802H4000-OH3 (CH2) 1aQ OOO02H4S OHz O
It was determined to be HOOOOa Ha--81(0OH3)3.

Example 5 Polymer 2 having SH groups at both ends obtained in Reference Example 2 was placed in a 1 t reaction flask similar to that used in Example 1.
44,! i'.

OH3 Organosilane 28I with the formula OH=OOOOOHBi (OCR).

Organosilicone catalyst 3y and toluene 3 represented by
After reacting at 50°C for 3 hours, the presence of the organosilane was detected using a gas chromatograph, so it was determined that the reaction had finished, and then the reaction was carried out at 120°C/10/tn+i Hg. When toluene was distilled off under these conditions, 267g of viscous liquid was obtained.
was gotten.

This liquid has a viscosity of 970 Boes (25°C).

The refractive index is 1.4786 (25°C) - the specific gravity is 0.889, and the alkoxy group-containing U is set at a constant V of 0.11 mol/100g, and this elemental analysis value is the cmos Si method theoretical value (%) 78.79 13 .01 5.37 1
．． 79 1.04 3.47 Analysis value (%) 78.88
13.00 5.33 1,76 1,03 3.4
1, since the chart on the infrared spectroscopy meter of this product is as shown in Figure 5? H3 (OH30)3SiO3H60000H-OH2So2
H4-1000 (OH2), 6o00002H4802
H4Coo-OH3-(OH2)16ooaoo□H,5on2-0800
00. H6--81 (OCR3).

It was determined to be XX, which is shown in .

Example 6 The average composition synthesized in Reference Example 1 using the same apparatus as Example 1 was as follows.

H802H4000 (OH2), 600000□H48
Polymer 24 having mercapto groups at both ends represented by H
102 g of silane represented by formula 51 - 2 g of azobisisobutyronitrile - 340 g of toluene. ! After charging ilY and reacting at 80°C for 6 hours with stirring, the presence of the above silane was examined using a gas chromatograph. Since no silane was detected, the reaction was judged to have been completed, and then the reaction was carried out at 120°C/1
When toluene was distilled off under conditions of 0 mmHg, 340 g of a viscous liquid was obtained.

This liquid has a viscosity of 400 Boes (25°C), a refractive index of 1.4728 (25°C), a specific gravity of 0.891°, a methyl ethyl ketoxime group of 0.129 mol/100 g, and a single element analysis value of theoretical value (%). 74.7612.525.192.0
81.823.6311.16 Analysis value (%) 748
712.485, 152.091.813.6011.
09, and the chart using the infrared spectroscopy needle is shown in FIG. 6 (I).

The following formula % formula % (4

[Brief explanation of drawings]

All figures show infrared spectrophotometric charts.13. FIG. 1 shows Example 1. Figure 2 shows Example 2, Figure 3 shows Example 3, Figure 4 shows Example 4, and Figure 5 shows Example 5-6.
The figure shows a chart of the polymer obtained in Example 6. Patent applicant Shin-Etsu Chemical Co., Ltd. = 35-

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Here, R^1 is a divalent hydrocarbon group having 1 to 6 carbon atoms, R^
2 is a divalent hydrocarbon group having 1 to 12 carbon atoms or a divalent organic group having 4 or less carbon atoms containing a thioether bond, R^3 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R^4 is carbon A divalent hydrocarbon group having 2 to 8 carbon atoms or a divalent hydrocarbon group containing an ester bond having 4 to 8 carbon atoms, X is a hydrolyzable group, a is 0, 1 or 2, m is 50 to 400, l is 0 to 20, and k is 0 or 1) A polymer having hydrolyzable groups at both ends. 2. General formula HO(CH_2)_mOH (m is 50 to 40
0), a mercaptoalkanoic acid represented by the general formula HS-R^1-COOH (R^1 is a divalent hydrocarbon group having 1 to 6 carbon atoms) and a general formula HOCOR^2COOH (R^2 has 1 to 12 carbon atoms
dicarboxylic acid represented by a divalent hydrocarbon group or a divalent organic group having 4 or less carbon atoms containing a thioether bond) to form a compound with the general formula HS-R^1-COO(CH_2)_m [OCOR^ 2
＿kCOO(CH_2)_m〕_lOCOR＾1-SH
(m is the same as above, l is 0 to 20, k is 0 or 1) A SH group-containing polymer is made, and then this polymer is expressed by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R^ 3 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, R^4 is a divalent hydrocarbon group having 2 to 8 carbon atoms or a divalent hydrocarbon group containing an ester bond having 4 to 8 carbon atoms, and X is A polymer having hydrolyzable groups at both ends is obtained by reacting it with an organosilane represented by a hydrolyzable group (hydrolyzable group) to obtain a polymer represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Production method.