JPS6031343B2 - Crosslinkable halogen-containing polymer composition and its normal temperature/pressure crosslinking method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for crosslinking a halogen-containing polymer at room temperature and pressure.

Conventional methods for crosslinking halogen-containing polymers, such as chloroprene rubber, chlorinated polyethylene rubber, chlorosulfonated rubber, and polyvinyl chloride, include sulfur vulcanization, chlorinated sulfur vulcanization, peroxide crosslinking, metal compound crosslinking, Amine crosslinking methods, halogen compound crosslinking methods, aldehyde crosslinking methods, etc. are known.

Among these, the sulfur vulcanization method, the peroxide crosslinking method, and the metal compound crosslinking method are generally widely practiced. However, all of the widely practiced methods described above require a high temperature of 100° C. or higher for crosslinking, and the required crosslinked product cannot be obtained at room temperature and pressure.

For example, in the sulfur vulcanization method, even when a vulcanization accelerator is used, sufficient vulcanization does not occur if the vulcanization temperature is below 100°C, and in the case of low unsaturated or saturated rubber, sulfur vulcanization does not occur. It cannot be vulcanized by a method. The peroxide crosslinking method, which uses organic peroxides such as dicumyl peroxide and penzoyl peroxide, has the advantage of being able to crosslink low unsaturated rubbers and saturated rubbers, but the decomposition of the organic peroxides Crosslinking is not possible at temperatures below (for example, 17rC for dicumyl peroxide), and if an organic peroxide with a low decomposition temperature is used, crosslinking may occur during operations such as blending and kneading. This makes it difficult to put it into practical use. Further, in the metal compound crosslinking method using zinc oxide, magnesium oxide, zinc oxide, etc., a sufficient crosslinked product cannot be obtained at a temperature of 100° C. or lower even if known excellent vulcanization accelerators are used in combination. This invention provides a method that enables crosslinking at normal temperature and normal pressure, which was impossible with conventional methods. A halogen-containing polymer composition that can be crosslinked at room temperature and under normal pressure is blended, and '2) a mercapto group-containing alkoxysilane compound represented by the following general formula 1 and a diamine compound represented by the general formula □.

The present invention relates to a method for crosslinking a halogen-containing polymer, in which alkoxysilane is grafted onto a genpolymer, and then this is brought into contact with water containing a silanol condensation catalyst to cause silanol condensation. General formula I HS-R-
Si(OR)3 General Formula B R2N-R'-NR2 In the above general formula, R and R'' are (CH2)n or R' is an alkyl group having 1 to 4 carbon atoms, R ''' indicates 1 day, 1 CH3, 1 C2 day 5.

This invention will be explained in detail below. This invention first involves adding a diamine compound represented by the general formula R2'''N-R''-NR2 to a halogen-containing polymer (where X is a halogen atom) with the general formula HS-R'-Sj(OR')3. The silane compound shown is crafted to obtain a mercaptoalkoxysilane grafted polymer.

This grafting is defined by the following chemical reaction formula. Any known method can be used for this grafting, but
In general, there are two methods: a kneading method in which a halogen-containing polymer, a silane compound, and a diamine compound are kneaded together, and a kneading method in which a halogen-containing polymer and a silane compound are first kneaded, and then the mixed material is brought into contact with a diamine compound. The law is well practiced.

Even in the case of using the above-mentioned method of deviation, crosstalk is preferably performed at a temperature as low as possible, for example, 10,000 ℃ or less. 100
Drilling at temperatures higher than 0.0° causes inconveniences such as the mercapto group-containing alkoxysilane compound scattering and the halogen-containing polymer decomposing.

Crosstalk can be accomplished using a solvent. Generally, it is preferable to carry out kneading without using a solvent. When a solvent is not used, it is preferable to intimately mix the halogen-containing polymer and the silane compound using, for example, a two-roll mixer or an extruder. The amount of the silane compound used in the present invention varies depending on the desired degree of crosslinking, but generally when the degree of crosslinking is 70% or more, it is preferably 5 to 15 parts by weight based on 10 parts by weight of the halogen-containing polymer. ~7.5 parts by weight. Further, the amount of the diamine compound used in this invention is proportional to the amount of the silane compound normally used. However, the degree of crosslinking and mechanical properties of the halogen-containing polymer can be adjusted by changing the amount of the diamine compound used within the range of the chemical equivalent with the silane compound. For example, FIG. 1 shows 5 parts by weight of r-mercaptopropyltrimethoxysilane or 1 part by weight of r-mercaptopropyltrimethoxysilane as diamine and mercaptoalkoxysilane in 10 parts by weight of a halogen-containing polymer (CI amount 35%, Mn=2×1). It shows the insolubilization rate (crosslinking degree) of the crosslinked product obtained when the amount of hexamethylene diamine blended as diamine was changed to 0.5 to 5 parts by weight in two types of compositions containing The figure shows the tensile strength of those crosslinked products and the third
The figure shows the growth rate. In this invention, the amount of diamine added to the crosslinking composition can be adjusted by soaking it in a diamine solution and soaking time. For example, Figures 4 to 6 show halogen-containing polymers (CI content 3).
Press sheets each having a thickness of 1 skin were made from two types of compositions in which 5% or 1 part by weight of r-mercaptopropyltrimethoxysilane was blended with 100 parts by weight of Mn; This graph shows the relationship between the soaking time in geltylene triamine, the insolubilization rate (crosslinking degree), tensile strength, and elongation rate when the press sheet is soaked in geltylene triamine and then the press sheet is soaked in water. be. The halogen-containing polymer in this invention is an organic polymer compound containing one or more halogen atoms (F, CI, 1, At) in the molecule, such as chlorinated polyethylene, chloroprene, chlorosulfonated Examples include polyethylene, polyvinyl chloride, polyvinylidene chloride, and the like. General formula HS-R-Si (OR
) As the mercaptoalkoxysilane represented by 3,
Aliphatic mercaptoalkoxysilane or aromatic compound in which R is (CQ)n (where n' is an integer from 1 to 10), or, and R' is CnH2n+, (where n is an integer from 1 to 4) Mercaptoalkoxysilane is a typical example.

Next, the mercaptoalkoxysilane graft polymer (hereinafter referred to as "graft polymer") obtained by the above grafting
That's what it means.

) is formed by extrusion or other forming means, and then the formed object is crosslinked by exposure to moisture in the presence of a silanol condensation catalyst. The silanol condensation in this invention is generally well known and is defined by the following chemical reaction formula. Here, R is (CH2)n (however, n is an integer of 1 to 10) or, and R is represented by C2M (however, n is an integer of 1 to 4).

The silanol condensation catalyst is a halogen-containing polymer (hereinafter referred to as "polymer") before being converted into a silane compound.

) or grafted polymers, or may be blended before or during molding by the above-mentioned extrusion or other molding means, or in some cases, a silanol condensation catalyst may be present after molding to achieve the desired effect. can. The silanol condensation catalyst used may be used alone or in the form of a masterbatch in which a large amount is mixed in a polymer or graft polymer. As a method of exposing the molded product to moisture, a method of crosslinking with moisture present in the atmosphere can be used, but if desired, there are also methods of using an atmosphere with increased humidity or a method of immersing it in water. The ambient temperature can be increased to speed up the crosslinking rate. Examples of the silanol condensation catalyst used in this invention include commonly known metal salts of carboxylic acids, organometallic compounds such as titanium chelates, alkyl titanate esters, and alkyl zirconate esters, organic bases, and organic acids. , specific representative examples include dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, dibutyltin octoate,
Tin, stannous oleate, lead octoate, zinc 2-ethylhexonate, cobalt naphthenate, cobalt octoate, iron 2-ethylhexonate, bis(acetylacetonyl) diisopropyl titanate, diisopropyl dititanium di(ethylacetoacetate) ), tetrabutyl titanate, tetrabutyl zirconate, ethylamine, hexylamine, dibutylamine, piveridine, triethylenediamine, octodecylamine acetate,
Examples include P-toluenesulfonic acid and acetic acid. Among these, preferred catalysts are dibutyltin dilaurate and dibutyltin acetate. As explained above, in the present invention, a silane compound having a mercapto group is made into a halogen-containing polymer, and the resulting grafted product is exposed to moisture in the presence of a silanol condensation catalyst.

Therefore, according to this invention, the halogen-containing polymer is
A crosslinked product can be easily and reliably crosslinked at a temperature of 10,000°C or less, and has good heat resistance. Incidentally, an organic metal compound, an inorganic metal compound, or a mixture thereof that is generally used as a stabilizer can be added to the polymer or graft polymer. Examples of this invention will be described below. Example 1 [Composition] This invention Comparative example 1 Chlorinated polyethylene (CI=35%, Mn=2×1 pi) 100 1〇〇r-mercaptotrimethoxysilane 1○ 1○ Hexamethylene diamine 5 0 The above composition was kneaded with an 80q0 roll for about 5 minutes, and pressed under 100q0 for 5 minutes to produce a press sheet with a thickness of 1 skin. After leaving this in a desiccator for a day and night, it was mixed with a 3% dibutyltin dilaurate aqueous solution of 60do. After thoroughly drying, the insolubilization rate and mechanical properties were measured.

[Measurement results] Those of this invention Comparative example Insolubilization rate (%) 80 0 Tensile strength (k9
/fence) 2.48 0.88 Growth rate (%)
320 780 Example 2 [Composition] According to this invention Comparative example 1 Chlorinated polyethylene (CI=40%, Mn=15×1) 100 10○ r-mercaptotrimethoxysilane 10 5 Hexamethylene diamine 5 0 Above The composition was kneaded with a roll of 8,000 for about 5 minutes, and pressed under 10,000 for 5 minutes to produce a press sheet with a thickness of 1. After leaving this in a desiccator for a day and night, 60 qo of 3% dibutyltin diurate was added. The samples were immersed in an aqueous solution for 1 hour, and after sufficiently drying, the retention rate and mechanical properties were measured.

[Measurement results] Those of this invention Comparative example Insolubilization rate (%) 85 2 Tensile strength (k9/
Secret) 2.55 0.80 Growth rate (%)
280 800 Example 3 [Composition]
Comparative Example 1 Chlorinated polyethylene (CI=40%, Mn=15×1 pi) 100 100 r-Mercaptotrimethoxysilane 1○ ・〇Dipropylenetriamine 5 Knead for 5 minutes under 10020
A pressed sheet with a thickness of 1 was prepared by applying pressure for 1 minute, and after being left in a dissicator for a day and night, it was immersed in a 3% dibutyltin dilaurate aqueous solution of 6000 for 1 hour, and after being sufficiently dried, the infusibility rate and mechanical properties were determined. was measured.

[Measurement results] Those of this invention Comparative example Insolubilization rate (%) 83 2 Tensile strength (k9/
2.50 0.78 Growth rate (%)
300 780 Example 4 [Composition]
Comparative Example Chloroprene rubber (
Neoprene W) 100 100 r-Mercaptotrimethoxysilane 10 10 Dipropylenetriamine 50 The above composition was kneaded for about 5 minutes with an 8000 roll, and pressed for 5 minutes under 100oo to form a press sheet with a thickness of 1. After leaving it in a desiccator for a day and night, it was immersed in a 3% dibutyltin dilaurate aqueous solution of 6000, and after sufficiently drying, the solubilization rate and mechanical properties were measured.

[Measurement results] Those of this invention Comparative example Insolubilization rate (%) 90 0 Tensile strength (k9/
2.45 0.45 Growth rate (%)
350 750 Example 5 [Composition]
Comparative Example Chlorinated polyethylene (CI=40%, Mn=15×1 pi) 10○・〇〇r-Mercaptotrimethoxysilane 50 The above composition was kneaded with a roll at 80°C for about 5 minutes. , 100
A 1 willow thick sample was prepared by pressurizing for 5 minutes under oC, soaked in 40 qo anhydrous gelylene triamine for 3 hours in an autoclave, then the sample was taken out and the surface was washed with distilled water. The sample was soaked in a 3% aqueous dibutyltin dilaurate solution of 6000 for 12 hours, and after sufficiently drying, the infusibility ratio and mechanical properties were measured, and the results were as follows.

[Results from Oroyama] Comparative example Insolubilization rate (%) 80 2 Tensile strength (k
9/Secret) 2.00 0.65 Growth rate (%
) 330 620 Example 6 [Set
Comparative example Chlorinated polyethylene 100 100 r-mercaptotrimethoxysilane 5 0 The above composition was kneaded for about 5 minutes with an 8000 roll,
A sample with a thickness of 1 skin was prepared by pressurizing it under 0q○ for 5 minutes, and after immersing it in 4000 anhydrous gelylene triamine for 3 hours in an autoclave, the sample was taken out and the surface was washed with distilled water. , 6000 in a 3% dibutyltin dilaurate aqueous solution for 12 hours, and after sufficient drying, the retention rate and mechanical properties were measured, and the results were as follows.

[Measurement results] Those of this invention Comparative example Insolubilization rate (%) 80 0 Tensile strength (k9
/fine) 2.40 0.72 Elongation rate (%)
330 750 Example 7 [Composition]
Products of this invention Comparative example Chloroprene rubber (Neobrene W) 100 10○ r-mercaptotrimethoxysilane 50 The above composition was mixed with a roll of 8000 for about 5 minutes, and 1
A sample with a thickness of 1 rib was prepared by pressurizing for 5 minutes under 00 qo, and after soaking in 40 oo of anhydrous gelylene triamine for 3 hours in an autoclave, the sample was taken out.
The surface was washed with distilled water, immersed in a 3% dibutyltin dilaurate aqueous solution of 6000 for 12 hours, and after thorough drying, the insolubilization rate and mechanical properties were measured, and the results were as follows.

[Measurement results] Those of this invention Comparative example Insolubilization rate (%) 85 0 Tensile strength (k9
/ rib) 2.30 0.50 Elongation rate (%)
400 750

[Brief explanation of drawings]

Figures 1 to 3 show the relationship between the amount of diamine in the composition of the present invention, the insolubilization rate (degree of crosslinking), the tensile strength, and the elongation rate. Diamine soaking time and insolubilization rate of the composition molded product in the invention,
This figure shows the relationship between tensile strength and elongation. In the figure, the curve marked with -, 1, 1, and - indicates the case where the amount of the silane compound blended is 10 parts by weight, and the curve marked with 1 o-o-o- indicates the case where the amount of the silane compound blended is 5 parts by weight. Fig. 2 Fig. 3 Fig. 4 Fig. 5 Fig. 6

Claims (1)

[Scope of Claims] 1. A crosslinkable halogen-containing polymer composition comprising a halogen-containing polymer, a mercapto group-containing alkoxysilane compound, and a diamine compound. 2. The crosslinkable halogen-containing polymer composition according to claim 1, wherein the mercapto group-containing alkoxysilane compound is contained in an amount of 1 to 15 parts by weight based on 100 parts by weight of the halogen-containing polymer. 3. The crosslinkable halogen-containing polymer composition according to claim 1, wherein the diamine compound is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the halogen-containing polymer. 4 A composition consisting of a halogen-containing polymer, a mercapto group-containing alkoxysilane compound, and a diamine compound
A method for crosslinking a halogen-containing polymer at normal temperature and pressure, which comprises kneading the polymer at a temperature of 0° C. or lower and then contacting it with moisture. 5. A method for crosslinking a halogen-containing polymer at room temperature and at normal pressure, which comprises immersing a composition comprising a halogen-containing polymer and a mercapto group-containing alkoxysilane compound in a liquid diamine compound, and then bringing it into contact with moisture.