JPS60233133A - Crosslinkable polymer composition - Google Patents

Abstract

PURPOSE:A composition crosslinkable with water without requiring a specific device, having improved heat resistance, chemical resistance, mechanical strength, elasticity, etc., obtained by reacting an amino group-containing polymer with a specific hydrolyzable organosilicon compound. CONSTITUTION:The titled composition obtained by reacting an amino group- containing polymer with a hydrolyzable organosilicon compound such as 3- isocyanatopropyltriethoxysilane shown by the formula (R and R'' are hydrocarbon; R' is hydrocarbon or hydrocarbon containing at least one hetero atom of nitrogen, oxygen and sulfur; X is hydrolyzable group; n is 1, or 2; m is 1, or 2; m+n<=3; a is 0-2).

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to crosslinkable polymer compositions.

[Conventional technology and problems]

There are various methods for crosslinking polymers, but in recent years, nine methods have been attracting attention that utilize the hydrolytic crosslinking properties of organosilicon compounds. However, a crosslinkable polymer in which a crosslinkable organosilicon compound is bonded to the amino group of the polymer molecule is not yet known. In particular, compositions in which a branched hydrolyzable organosilicon functional group is bonded to a 7-mino group of a polymer, or both an organosilicon functional group and an incyanate group are bonded to a 75-mino group of a polymer as a crosslinkable functional group. No known compositions are known.

[Means for solving problems]

In view of these points, the present invention provides that one or two terminals of the functional groups of a linear or branched hydrolyzable organosilicon compound are incyanate groups, and bonded to the amino groups of the polymer. It has been discovered that a crosslinkable polymer composition of 1 can be efficiently obtained.

That is, 1. the present invention comprises a polymer having an amino group and a polymer having the general formula (Z
) A crosslinkable polymer composition is provided, which is obtained by reacting a hydrolyzable organosilicon compound represented by:

[Effect]

The polymer having an amino group used in the present invention has at least one of an amide bond, an ester bond, an ether bond, a urethane bond, a urea bond, and a carbon bond in the main chain,
Polymers having amino groups at the terminals or side chains are produced by known methods.For example, copolyamides having amino groups at the terminals are produced by polycondensation reaction of dicarboxylic acid and diamine, or by dicarboxylic acid chloride. It is produced by external polycondensation reaction of diamine and diamine. By adding an excess of the siaquine component, most of the terminal ends of the cyanopolymer become amino groups. Alternatively, three or more amino groups can be introduced into one molecular chain by copolymerizing a small amount of triamines such as diethylenetriamine or pentamers of trimellitic acid or fatty acids to create a branched polyamide. The activated unsaturated double bonds of polyamide are copolymerized with a small amount of unsaturated dicarboxylic acids (chloride) such as fumaric acid (chloride), itaconic acid (chloride), and citracone l' (chloride) as dicarboxylic acid (chloride) components. It is also possible to introduce amino groups into the side chains of the polymer by Michael addition of diamines.

Modified polyamides can also be used in the present invention, such as flexible polyetheramides with ether bonds obtained by copolymerizing polyalkylene glycol diamines having amino groups at both ends.

Furthermore, by radical copolymerizing (meth)acrylamide with a vinyl monomer having an ethylenically unsaturated double bond, a dead polymer having a 7-mino group in the side chain can be obtained.

X in the organosilicon compound represented by the general formula (I) used in the present invention may be a hydrolyzable group. Examples of such groups include alkoxy, cy groups, alkenyloxy groups, acyloxy groups, aminooxy groups, phenoxy groups,
Examples include thioalkoxy group, oxime group, andosilyl group, and the like. A hydrolyzable organosilicon compound having an isocyanate group represented by the general formula (X) can be obtained by, for example, inocyanating an organosilicon compound having an amino group and represented by the following general formula (I) with phosgene, or (The phantom amino group is a chloro group.

It can be obtained by reacting a certain chloroalkylsilane with potassium isocyanate or the like.

R: (H2'-R book"'-"'-x5-@)B (
If) (R, R', R'', X, n, m, a are as defined above) An example of a compound thus obtained is 3-isocyanatopropyltriethoxysilane.

−5= 3-Incyanatopropyltrimethoxysilane.

Examples include 5-isocyanatopropylmethyljethoxysilane. First, the compound represented by the general formula (I) is prepared by combining an organosilicon compound represented by the following general formulas 〇I) to (to) having an amino group, an inno group, or a mercapto group with a diisocyanate compound or a triisocyanate compound in a one-to-one manner. It can also be obtained by carrying out an addition reaction at a ratio of 2 to 10.

R; n2FIt#-5i-x, -aol R: R; ll5-u"-al-x, -, (V) (where R", a is as described above, R", R#, R' is an aliphatic or aromatic hydrocarbon group.

The stock R' may contain different elements such as nitrogen, oxygen, and fluorine. k and J are integers and when %ke=00, no 2S
When k=1) Company 10) 6- As an example of a compound represented by the general formula (匍~(V)), N
-(5-acryloxy-2-hydroxypropyl)-3
-7 minopropyltriethoxysilane, 4-72 butyldimethylmethoxysilane, (aminoethylaminomethyl)7enethyltrimethoxysilane, N-(2-aminoethyl)-3-7i nopropylmethyldimethoxysilane, N-2-72 noethyl-3-aminopropyltrimethoxysilane, N-2-aminoethyl-5-aminopropyltris(2-ethylhexoxy)silane, p-aminophenyltrimethoxysilane, 3-7 minobrovir dimethyl Ethoxysilane, 3-aminopropylmethyljethoxysilane, 3-a is nobrobiltriethoxysilane,
5-aminopropyltrimethoxysilane, pix(!1-
()+7ethoxysilyl)Flohir]amine, bis[!
5-()rimethoxysilyl)propyl]ethylenediamine, 3-mercaptopropylmethyldimethoxysilane,
3-Mercaptopropyltrimethoxysilane, 5-mercaptopropyltriethoxysilane, N-methylaminopropyltrimethoxysilane, Methyl[2-(3-trimethoxysilylglobylamino)ethylamine2-5-
Globionate 5y- (par 70 looctanilade)
Examples include propyltriethoxysilane, 3-ureidopropyltriethoxysilane, and N-phenylinobrobyltrimethoxysilane.

Di- or triisocyanate compounds used in the present invention include hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-bis(isocyanatomethyl)
Cyclohexane, trimethylhexamethylene diinocyanate, lysine isocyanate methyl ester, hexamethylene diisocyanate biuret, trimethylolpropane/hexamethylene diinocyanate adduct,
Toluene diisocyanate.

44'-diphenylmethane diinsyanate, 1°5-
Naphthalene diincyane),! ,! '-dimethyl-4
．． 4'-diphenylene diisocyanate.

Examples include 2.4-toluene diisocyanate dimer and trimethylolpropane/toluene diisocyanate addition.

The hydrolyzable organosilicon compound having the above general formula (@ or (expressed by a cup) group or imino group can be converted into a diisocyanate compound or triisocyanate compound in a suitable solvent without active hydrogen or without using a solvent. When mixed with a compound, it reacts easily at room temperature.To complete the reaction, it may be heated to about 60°C.Also, if the general formula (
Since the hydrolyzable organosilicon compound having a mercapto group represented by V) has a low reactivity with an incyanate compound, it is necessary to react it at a temperature of 50 to 100° C. in the presence of a basic catalyst.

The progress of the reaction can be confirmed by quantifying the proportion of residual incyanate groups. The reaction proceeds easily by dissolving the polymer in a solvent free of active water and adding the above-mentioned hydrolyzable organosilicon compound at a temperature of 20 to 150°C. The reaction can also be carried out in a short time by heating and melting the polymer at a temperature equal to or higher than its melting point and dropping the above-mentioned hydrolyzable organosilicon compound.

〔Effect of the invention〕

In the crosslinkable polymer composition of the present invention, the organosilicon groups bonded to the terminal and/or side chains of the polymer are hydrolyzed in the presence of water to form silanol groups, which further undergo a condensation and dehydration reaction. It changes into a crosslinked product with siloxane bonds.

Further, in places where inocyanate groups coexist, crosslinking occurs accompanied by a hygroscopic crosslinking reaction of the isocyanate groups. To promote the crosslinking reaction, an organotin catalyst such as dibutyltin laurate, diptyltin octoate, diptyltin oxide, or an organotitanate catalyst such as tetrabutoxytitanium or tetraisopropyloxytitanium is added to the polymer at a concentration of 0.00%.
It is also possible to add 1 to 5% by weight and 10% by weight. This crosslinking reaction proceeds with moisture in the air or by immersion in (hot) water, so 1! #Extremely economical as no special crosslinking reaction equipment is required.

Since the crosslinkable polymer composition of the present invention does not crosslink in the absence of water, it can be used in various ways, such as molding, I-ting, and adhesion, in the same way as non-crosslinkable polymers.

The above crosslinking reaction occurs in the presence of moisture.

It exhibits excellent heat resistance, chemical resistance, mechanical strength, and elasticity, so it has high utility value in fields where these properties are required.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.0 Example 1 (Synthesis of a hydrolyzable organosilicon compound having an incyanate group) Hexamethylene diisocyanate 2 & 2s parts by weight (O, 1S mol) Chloroform 255.52 parts by weight Pour into a separable flask and stir at room temperature.
-Aminoprobyltriethoxysilane 5L 15 parts by weight (
o, 1 s mol) was added dropwise over 15 minutes, and the reaction was continued for an additional 60 minutes. The weight percent of the remaining isocyanate groups in the reaction product was determined by the diptylamine method and found to be 2.05%. Hexamethylene diisocyanate and 5-
This is 95% of the theoretical residual isocyanate amount when aminopropyltriethoxysilane is reacted in a 1:1 ratio. Therefore, it can be seen that the compound represented by the formula is produced.

FIG. 1 shows the infrared absorption spectrum of this compound (A), and FIG. 2 shows the MMR spectrum. -The infrared absorption spectrum includes absorption based on incyanate group in z2aos-'',
i, 5sos-'', 1720-1425 (absorption based on urea bond to II-1, 1105-1080 plow-1%7
Absorption based on alkoxysilyl group is observed in 8 Os-'0, +0.5-0.8 ppm K in NMR spectrum
Peak of methylene group in contact with BiKil, 1.1-1.4
Methyl group of ethoxy group in ppm,! 1.7-4.2pp
A peak of methylene group of mg ethoxy group was observed, and 5.
A proton peak of the urea group appears around 6 ppm.

(Synthesis of crosslinkable polymer) C-cabu-lactam '4B 2.9 parts by weight (2 & 0 mol%) Ryubasin@2!104 # (11,4#) Decanedicarboxylic acid 242.5 1 (li, 4 g)
Isophthal II 189.4 1 (11,41) was placed in a separable flask, 474.1 parts by weight (40.8 mol%) of hexamethylenediazene was added dropwise while the temperature was raised, and the mixture was heated under 2so ICK under a phonetic atmosphere for 1 hour. The reaction was carried out under pressure. Thereafter, the pressure was reduced to OsamHH and the reaction was continued for 1 hour to obtain a co-heavy metal boria resin. The acid value of the boriyad resin is Q KOHq/? , the total fin number is 45.6 K
OHw9/f % According to the ring and ball method 1! The softening point measured by I-C was 105°C.

100 parts by weight of the polyamide resin (amino group: 0.0777
Equivalent) 400 parts by weight of dehydrated dimethylformamide was charged into a separable flask and heated to 70°C to dissolve.

ζζ is a chloroform solution of the above isocyanated organosilicon compound (A) 167.2F (isocyanate group
, oa16MA amount) was added dropwise over 15 minutes, and the reaction was carried out for 1 hour while distilling off chloroform. Thereafter, 400 parts by weight of dehydrated acetone was dropped while lowering the temperature to precipitate the polymer, and the acetone washing was repeated. and! Vacuum drying was performed at IO° C. for one day to obtain a modified boriaod resin in the form of a white powder. Since the modified boria resin was completely dissolved in benzyl algol at room temperature, it was confirmed that it was not crosslinked during the manufacturing stage. The modified polyamide resin powder was treated in purified water for 2 hours, dried under vacuum at room temperature, and then its solubility in benzyl alcohol was examined and the insoluble portion was found to be 9B%. Further, even when the resin □ after vacuum drying was heated to 200°C, it did not melt. Therefore, it was confirmed that the crosslinking reaction progressed due to the seawater treatment.

Example 2 (Synthesis of a hydrolyzable organosilicon compound having an isocyanate group) 30.0 parts by weight (0,178 mol) of hexamethylene diisocyanate and 55.0 parts by weight (0,178 mol) of 3-mercaptopropyltrimethoxysilane. The mixture was placed in a separable flask, heated to 70° C., 0.0002 mol of triethylamine was added, reacted for 60 minutes, and cooled after death.

The amount of residual incyanate groups in the reaction product is 11.1 wt%
Met. This is 96% of the theoretical remaining incyanate amount when the above reaction proceeds at a ratio of 1:10. Therefore, it can be seen that the compound represented by the formula was obtained. Figure 5 shows the infrared absorption spectrum of this compound (B), and Figure 4 shows the NMR spectrum.
The spectrum is shown. 22yo for infrared absorption spectrum
a-' Absorption based on ItC isocyanate group, 3310
Absorption based on an amide bond is observed at aa'''1.1675 to 1655fi-1, and absorption based on an al;xysilyl group is observed at 1085 as-' and 815m-1.

(Synthesis of crosslinkable polymer) C-caprolactam 282.9 parts by weight (25.0 mol%) Adipine 51166.6 1 (11,4#) Sebacin $ 2so, 61 (11,4#) Decanedicarboxylic acid 2615 g A copolymerized polyether ad resin was synthesized in the same manner as in Example 1 using a charging ratio of (11,4#) hexamethylene diamine 426.5# (56,7#). The acid value of the resin is 6.59 KOHsl
v/f, total amine value was 4Q, 9 KOHq, and softening point was 140°C.

100 parts by weight of the resin (0.0727 equivalents of amino groups), 400 parts by weight of dehydrated dimethylformamide, isocyanated organic silicate compound (B) (0.0 parts of isocyanate groups)
A trimethoxysilyl-modified polyetheramide resin was obtained by carrying out the reaction in the same manner as in Example 1 at a ratio of 28.89 parts by weight (764 parts by weight). Measured in the same manner as in Example 1, the percentage of insoluble parts was 0% before seawater treatment and 99% after seawater treatment.
．． The resin after treatment with 5% boiling water showed no melt fluidity even when heated to 200°C, and 90 Example 3 (Synthesis of hydrolyzable organosilicon compound having an isocyanate group) Hexamethylene diisocyanate<, Yulet Body (Sumitomo Bayer Urethane Sumishult 3200) 54.8
Part by weight (0.10 mol) 5-7 onoglobiltrimethoxysilane 35.9 parts by weight (0.20 mol) Chloroform 362.6 parts by weight A reaction was carried out in the same manner as in Example 1.

The amount of incyanate groups in the reactant was 0.92%. As shown in the following formula (0), one molecule contains two trimethoxysilyl groups and one incyanate group at 17-.
A chloroform solution of organic silicon compounds was obtained.

0 0 (Synthesis of crosslinkable polymer) Adipic acid 219.2 parts by weight (ts, o mol%) Acelaic acid Gol, 2# (16, RO I) Decanedicarboxylic acid S6B, 5# (16,0#) xamethylene Schiff<y! 1115.8# (29,0#
) Piperazine zzto # (z6.o #) in the same manner as in Example 1 to synthesize a copolyamide having amino groups at the terminals. The acid value of the copolyamide resin is 0.05 POHq/f, and the amine value is 58.7.
KOH No./f and softening point were 145°C.

Next, 18-terephthalic acid 277.5 parts by weight (16,74%) isophthalic acid @ 167.8 1 (10,1#) adipic acid 172.4 # (11,8#) 1,4-butanediol sa &2#(34,2#) neopentyl glycol 250.2 g (2110z) was charged into a separable flask K. The temperature was raised to 21°C to perform a dehydration condensation reaction, and when a predetermined amount of water was distilled off. The amount of carboxyl group in the acid component of tetrabutyl titanate is 1f! [On the other hand, add too much ppm to 250
The temperature was raised to ℃. Then, the pressure was gradually reduced and finally a polycondensation reaction was carried out for 50 minutes under a vacuum of S to Hg to obtain a copolymerized polyester resin. The acid value of the copolymerized polyester resin is 0.14 KOHtq/t, and the hydroxyl value is a 1
:2KOHq/fs Softening point was 82°C.

The copolymerized polyester resin 271.4 parts by weight (0.1 parts by weight)
mol), dehydrated dimethylformamide 30 & 0 1 was placed in a separable flask, heated to 100°C and dissolved, and then 53.6 parts by weight of hexamethylene diisocyanate (0,
2 mol) and react for 2 hours and 10 minutes. The analytical value of isocyanate at this time was 1.39% by weight, and the theoretical isocyanate amount (1, Sa weight%) K when both ends of the copolymerized polyester were incyanated was a circle.

In another separable flask, 2.0 parts by weight (0.2 mol) of the copolymer f-boriad resin SB was dissolved in 582.0 parts by weight of dehydrated dimethylformamide by heating at 70°C. A dimethylformamide solution of the isocyanated copolymerized polyester resin was added dropwise over 1 hour, and the mixture was further reacted at 70°C for 1 hour. At this time, the analysis value line of incyanate is 0%, and the azun value is 4.0KOH1
It was f. In this way, a polyand-fist polyester/polyamide type block copolymer having A and No groups at both ends was obtained.0 Added to this block copolymer solution was a 20% chloroform solution of the isocyanated organosilicon compound (0).
47.2 parts by weight was added dropwise for 1 hour, and the reaction was continued for another 1 hour.The analytical value of the isocyanate of the solution was 0.02% and the aion number was 0. The solution was cast onto release paper.

A white film was obtained by drying with hot air at 170°C for one day.

The film was heated in dimethylformamide at 70° C. for 6 hours and 9 did not dissolve. Furthermore, it was confirmed that the polymer did not melt even when heated at 200° C., making it an infusible and insoluble polymer.

A film produced by similarly casting the block copolymer solution before reacting with the incyanated metal organosilicate (0) was redissolved when heated in dimethylformamide at 70°C.

Furthermore, the melting point measured by differential thermal analysis at 10°C and a heating rate of 7 minutes was 15s'C.0 Example 4 (Synthesis of hydrolyzable organosilicon compound having isocyanate groups) Trimethylolpropane/toluene diisocyanate Adduct (Coronate L manufactured by Nippon Polyurethane Industry ■, solid content 75%, isocyanate = 12.58%) 19.6 parts by weight (0.1 oomol) of 21-3-mercaptopropyltrimethoxysilane was charged into a separable flask for 60 minutes. The temperature was raised to .degree. C., 0.010 parts by weight (0,0001 mol) of triethylamine was added, and the mixture was allowed to react for 1 hour.The analytical value of isocyanate groups was 6.99%.9. This value was in close agreement with the theoretical value of 7.02% of the remaining isocyanate groups when one 5-mercaptopropyltrimethoxysilane was added to one molecule of the trimethylolpropane/toluene diisocyanate adduct. This compound is schematically represented by the following formula (D).

(Synthesis of crosslinkable polymer) C-caglolactam 2829 parts by weight (25 mol%) 2
2- Adipine II 16o, a parts by weight (11 mol%) Sepa'
/7 acid 2216 # (11#) decanedicarbone II 253.3 y (11#) hexamethylene cyanide 459.5 z (57,8z) 1,2-propanediamine B1.1z (4, l#) A copolyamide resin was synthesized using the same proportions as in Example 1. The acid value of the resin is 0.08 KOH/f, and the amber value is 5.
6.9 KOHtq/t, melting point determined by differential thermal analysis was 118 °C.

The copolymerized polyamide, 100 parts by weight of resin, (0 amino groups
．． 101 equivalents), dehydrated dimethylformide 500
Parts by weight were placed in a separable flask and heated to +70°C to dissolve the resin. Then, after adding 121.4 parts by weight (0.202 parts by weight of isocyanate group) of the solution of the incyanate-modified organosilicon compound (D) and reacting for 1 hour, the analytical value of isocyanate F was 1.58%. there were. While cooling the solution, 300 parts by weight of dehydrated acetone was added to 2
The modified boriad resin was precipitated by dropwise addition over a period of time, and after repeating filtration and washing with acetone, it was vacuum dried at 1z0°C for 1 day (step 7 to obtain a modified boriad resin in the form of a white powder.The melting point of the resin was The resin was completely dissolved in benzyl alcohol at home temperature.After the resin was treated with seawater in the same manner as in Example 1, it did not dissolve in benzyl alcohol and the insoluble portion was 96%. Furthermore, even when the resin after seawater treatment was heated to 200°C, it did not melt.

Example 5 Styrene 75 parts by weight (10.6 mol%) Acrylonitrile 190# (52.8#) Ethyl acrylate 255# (34.6#) Acrylamide 2. ?
1 # (0,49 #) toluene 555.41 The raw materials were charged into a separable flask and heated to 80°C to produce 2.2'-azobisisobutyronitrile 10.0
' parts by weight were added and a polymerization reaction was carried out for 6 hours. Then 3-
8.5 parts by weight (0.49 mol%) of isocyanatopropyltriethoxysilane was added dropwise over 15 minutes, and the reaction continued for an additional 60 minutes. This solution was cast onto a release paper and vacuum dried at 80° C. for one day to form a film having a thickness of 0.2 to 0.2S 1111. Furthermore, a part of the film was heated to 100°C.
The sample was boiled in purified water for 3 hours and dried with hot air at 100°C for 8 hours. And I was saddened by the next result.

[Brief explanation of the drawing]

Figure 1 shows the infrared absorption spectrum of the organosilicon compound obtained in Example 1, Figure 2 shows its NMR spectrum, Figure 3 shows the infrared absorption spectrum of the organosilicon compound obtained in Example 2, and Figure 4 shows the infrared absorption spectrum of the organosilicon compound obtained in Example 2. The figure shows the spectrum. Applicant's agent Kaoru Furuya 25-

Claims (1)

[Scope of Claims] A crosslinkable polymer composition obtained by reacting a polymer having an amino group with a hydrolyzable organosilicon compound represented by the general formula (1).阿(OON-R)(-R'-8i-X, a)m(I) (where R, R" is a hydrocarbon group, R' is a hydrocarbon group or one or more of nitrogen, oxygen, and sulfur) (Hydrocarbon group containing a different element, X is a hydrolyzable group, n is 1 or 2, m is 1 or 2, where m+n≦3, a is an integer from 0 to 2)