JPS6076505A - Manufacture of chlorinated ethylene polymer elastomer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to the modification of ethylene monomers.

[Background of the invention]

In elastomer theory, when -kL fatherly bonding of densified ethylene monomers, (a) solvent resistance, (b) osone body resistance, (
c) La+-u abrasion resistance, (d) weather resistance, (e) approximately -20
C.f)> is also an industrially attractive material because it is characterized by a number of desirable properties, including flexibility over a wide temperature range extending to about 120.degree. Therefore, the cured chlorinated ethylene 1 compound and compositions based thereon are
Due to the above-mentioned excellent properties, it is widely used in many applications, such as film materials, extrusion molded materials such as wires and cables, base polymers for flame-resistant compositions, and flexibility agents such as polyvinyl chloride polymers. There is.

Conventionally, chlorinated ethylene polymers have been produced by a solution method in which the polymer is reacted with a chlorinating agent in a solvent.

So-called solution processes require that the solvent be removed from the chlorinated polymer at the end of the reaction, generally by heating the reaction system to a temperature sufficiently high to drive off the solvent. but,
Chlorinated ethylene polymers tend to agglomerate when exposed to solvent temperatures, making handling and processing difficult.

[Purpose of the invention]

Therefore, an object of the present invention is to avoid the use of solvents and diluents, thereby solving the problems associated with their use, and to provide a homogeneously chlorinated granular nidistomer ethylene polymer with well-balanced properties. It's there. Since the chlorinated ethylene polymer of the present invention is granular, it is easy to handle and process.

[Description of the invention]

The chlorinated ethylene 1 compound of the present invention is prepared by applying a gaseous chlorinating agent to the chlorinated ethylene compound of about 0.87 to α92 mm in the absence of a solvent or diluent.
lil/cc, preferably 0,89~a, HFl/Ce
and pore volume o, 1~1 cc7g, generally 01
~a, 5. cc/4, more preferably 0°2-0.4
approximately 2.000 psi (141k
A particulate nidistomeric chlorinated ethylene polymer having a tensile modulus of less than about 10 g/σ2) and a crystallinity of less than about 10 inches is produced.

The chlorinated ethylene produced in this way (the union is uniformly chlorinated and elastic (elastomeric))
It has an excellent balance of properties comparable to commercially available chlorinated ethylene offshore bodies produced in the form of aqueous dispersions.

Ethylene polymers suitable for the purpose of the invention having the above-mentioned densities and pore volumes are ethylene-〇, ~C1l alpha olefin polymers obtained by reacting ethylene with at least one alpha monoolefin under low pressure. be. Such manufacturing methods are described in US Pat. No. 4,302,565, US Patent Application No. 4B0.296, and others.

Particularly desirable ethylene polymers for purposes of this invention have the density and pore volume described above, and further have about 50 to 99 moles of ethylene, preferably about 75 to 96 moles of ethylene, and about 1 to 50 moles of ethylene.
Morti, preferably about 4 to 25 moles -〇〇, ~C, alpha monoolefins (e.g. butene-1, butene-1,
pentene-1,4 methylpentene-1, hexene-1,
Contains heptene-1 and octene-1).

The more preferred ethylene polymers to be chlorinated according to the present invention are:

Approximately 200 to 1500 μm 1 preferably approximately 300 to 100
0 μm average particle size and about 10 to 30, preferably about 15 to 241 b/ft” (
(Ll 6-0.48, preferably 024-about 01-1
cc/9, preferably about 01-0.5 cc/9, more preferably about 0.2-0.4 cc/9, and about 0.87-0. q 29 /cc, preferably about 0
．． 89-o, and a density of 91 g/ee.

Processing time for gaseous #', clearing and stiffening agent is approximately 20 ps.
i (141 kg/♂), a crystallinity of less than 10 inches (preferably 0 to 5 inches), and about 5 to 55 wt%, preferably 15 to 40 wt%.
chlorinated ethylene 11 coalesce having a total chlorine content of .

This treatment appears to replace the known hydrogen atoms of the ethylene polymer with chlorine.

The actual time of processing is ethylene jlf coalesce to be chlorinated,
Depending on the chlorinating agent, temperature and pressure used, approximately 3 to
It will turn into light within 10 hours.

Generally, suitable temperatures are about 50-130°C, preferably about 50-100°C. The pressure at which the reaction is carried out is about 70 kg/σ2 from atmospheric pressure. However, in this case, the reactants or by-products must not be present under the reaction conditions. Generally, the higher the temperature and pressure, the shorter the reaction time.

The amount of chlorinating agent used to carry out the reaction is approximately 10-200w
t%, preferably about 20 to 100 wt% (based on the ethylene polymer to be treated).

If desired, an inert gas such as nitrogen may be used with the modifying gaseous chlorine gas to act as a fluidizing agent, dispersion aid, and heat sink.

The properties mentioned here were measured by the following method.

Density (,9/cc) - According to ASTM-D-1sos.

A plate was prepared and conditioned at 100° C. for 1 hour to bring it close to crystal equilibrium, and the degree of confinement was measured in a density gradient chamber.

Hole valley shape (cc/#)-ASTM-C-s99-toe
According to (4s).

Average particle size (μm) - Calculated from data obtained from classification analysis of a 500 g sample determined according to ASTM"D-1921 method A. Calculations were made by weight fraction remaining on the sieve.

Bulk Density (lb/ft”) - 1o from 95mm diameter funnel
10 without vibration to the o- scale ladle cylinder
>IC combination was added up to 0m/scale.

The bulk density was calculated from the difference between the part of the cylinder and the N light of the filled cylinder.

Crystallinity (%) - Measured using a DuPont 990 analyzer equipped with a pressure gradual scanning calorimeter (DSC) cell.

Tensile modulus (pst + k, 9/cyn”)
-4in x41nXO, o 20in (10cm
,X10crrLX0.51! A film of I+W) was pressure-molded at 130 to 150°C, and its secant modulus was determined according to ASTM-D-638.

Tensile strength P811 kg/crn'') - Similar film as determined by ASTM-D-658 at 411''.

Elongation at break (%) - similar film AS'l''MD
-658.

〔Example〕

Examples of the present invention will be explained below.

Unless otherwise specified, the ethylene polymer used as a starting material in the following examples was produced by the method described in US Pat. No. 4,802,96 (K).

Ethylene 1 is made of glass-lined stainless steel matahastelloy alloy (55% Ni, 117% Mo,
Chlorination was carried out using a reactor made of 16% Cr, 6% K'e and 4% N, equipped with a thermocouple and an electric U-shaped Hasty alloy stirrer.

The gaseous modifying agent was fed to the reactor using a Hastelloy down tube (2 crn diameter). Unreacted denaturant and HCI were vented into a distillation trap containing 25 g of aqueous NaOH. The gaseous modifier is about 15-450 psi
(t O~52 kg7am2) (CI under D pressure.

was supplied at a flow rate of 8 to 15 g/hr.

Approximately 200-1000 g of the polymer to be treated was charged into the reactor and heated by an external heater. No catalyst was used in these examples.

After charging the polymer into a reactor and heating it to the desired reaction mixture layer, the polymer was stirred with a stirrer and transferred to a gaseous state. ) Hayama Ki-ri
Samples were extracted from F. a and the chlorine content and crystallinity were measured. At the end of the reaction, the flow of the gaseous modifying agent is stopped and the reaction vessel is purged with nitrogen gas to remove any unreacted C.
The product was allowed to cool while removing 1□ and HCI by-products.

A 3aI granular low-density ethylene-butene-1 combination having the properties listed in the following table was chlorinated with chlorine gas (Sample A%B, Control 1).

Control IA B Density fr: (,!i'/cc) 0.9260.918
0.875 Crystallinity (skin) 50 44 13 Particle M (average pm) 400 500 400 Air volume (
Flash/77) 0.5 045 (J, 57 tensile strength psi) 2190 5540 290 (kq/my)
) (154) (244) (20) Growth rate (%)
460 983 920 Ethylene-butene-1 copolymer was chlorinated by reacting with C1 gas for about 8-14 hours at a temperature of 70-80°C (for seal 1 and sample A)
.

Further, in the case of sample B, the above temperature was set to 60°C. The results in Table I were obtained. Example 1 corresponding to samples A and B.
Set it to 2.

Table I Control 1 Control 2 Example 1 Example 2 Chlorine (%) 24. 5633 26 Crystallinity (%) 5 22 2.8 6.5 Elongation rate (%
) 930 765 900 1500 Note: Control 2 is a chlorinated polyethylene commercially available from The Dow Chemical Company. The chlorinated polymer of Control 1 is not an elastomer as evidenced by its high tensile modulus.

In contrast, the nidistomers prepared according to the present invention are found to have properties comparable to commercially available chlorinated polymers.

To further illustrate the need to use ethylene vehicle assemblies with defined pore volumes and densities, a Control 5 experiment was conducted using granular ethylene with the following properties:

Density (g/cc) 0.968 Crystallinity (%) 0.5 Average particle size (μm) 0.3 Porosity (CC/l) 0.3 This polymer was heated at 85 to 90°C with chlorine gas. A chlorinated polymer having the following properties was obtained by chlorination.

Table ■ Crystallization rate (ch) 89 <52 35 From the results in Table II showing the comparison period 6, just because the chlorinated 1 coalescence has a relatively high chlorine content does not mean that it will become the ela 2 tomer. I understand.

A similar experiment was conducted on Control 4, which consisted of a particulate ethylene-butene-1 copolymer having the following properties:

m [(&/ce) 0.9 s s Butene-1tS in sympathies (MOA/CH) Crystallization K (%) 5 & 5 Average particle diameter (μm) s o.

Porosity (''/g) o35 This copolymer was chlorinated at 90° C. using chlorine gas to obtain 1 μ of a chlorinated polymer having the properties shown in Table 3.

Table 1 River chlorine 0 11 17 25 30 (wt%) Crystallization rate 265 52 52 54 29 (%) Well, it's a rainbow-ih
The formula 4+Δ-intermediate, Ti1U1, and Sample A were prepared according to the method of U.S. Pat. No. 4,502,565.

The chlorinated ethylene polymers of the present invention are well known in the art.
- Can be cross-linked using peroxides such as cumel peroxide.

As described above, according to the present invention, it is possible to provide an excellent elastomeric chlorinated ethylene polymer or copolymer similar to that obtained by in-solution reaction using a gaseous chlorinating agent, and there are advantages in terms of the process. There are also many.

Procedural amendment (method) % formula % Indication of the case Patent Application No. 146166 of 1980 Name of the invention Relationship with the case of a person who amends the manufacturing method of chlorinated ethylene polymer elastomer Name of watch applicant Union Carbide Co., Ltd. October 50, 1980, ゛
- Φ number = = - Contents of the amendment to the specification subject to amendment No changes to the written MLC of the specification as attached)

Claims (1)

[Claims] 1.0.87~o, q2fl/Cc density and 0.1~1
2, characterized in that a particulate ethylene polymer having a pore volume of 0 cc/fl is reacted with a gaseous chlorinating agent.
A method for producing a particulate chlorinated ethylene polymer didistomer having a tensile modulus of less than 1,000 pat (141 yu/σ2) and a crystallinity of less than 10 pat. 2. The granular ethylene polymer is 0.1 to o, s cc
2. A method for producing a chlorinated ethylene 1-coupled distomer according to the above item 1, which is a ethylene-〇, iron C, and alpha olefin 10-coupled product having a pore volume of /9. 2. The method for producing a chlorinated ethylene polymer elastomer according to item 2 above, wherein the elastomer has a working weight of 0.89 to α91 fl/cc and a pore volume of 0.2 to 0.4 cc//l. 4. The method for producing a chlorinated ethylene polymer didistomer as described above, wherein the chlorinating agent is chlorine gas. 5. The method for producing a mono-enriched ethylene 1-polymer distomer according to item 1 or 2 above, wherein the ethylene polymer is an ethylene-butene-1 copolymer. 6. The chlorination is carried out at a temperature of 50 to 130°C.
Any one of item 1 to item 5 (((method for producing a chlorinated ethylene polymer elastomer described in item 1). Alternatively, the method for producing a chlorinated ethylene 35-coated elastomer described in Part 2.