JPS603418B2 - polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to impact-resistant polymer compositions based on copolymers of unsaturated nitriles, largely saturated rubbers (hereinafter referred to as highly saturated rubbers) and chlorinated polyethylenes.

Generally, unsaturated nitrile-based impact polymer compositions contain one or more monomers such as styrene, Q-methylstyrene, acrylonitrile, vinyl chloride, maleic anhydride, and/or one or more acrylates. It has a graft polymer that is graft-polymerized to.

A typical example of this type of polymer is ABS (a graft copolymer of styrene and acrylonitrile grafted onto (butadiene) rubber). The continuous phase of the polymer composition (
Because some of the monomers forming the matrix are grafted onto the rubber, these compositions exhibit high impact resistance even at low temperatures (-20°C). As for rubber, polybutadiene or its two related rubbers are increasingly being used.

Due to the high degree of backbone saturation of these rubbers, they exhibit a tendency to oxidize under the influence of light and/or molecular oxygen. The properties are severely degraded and therefore it cannot be used as is for outdoor applications.To solve this problem, the rubber in the polymer composition is replaced by a highly saturated rubber such as ethylene/propylene rubber or ethylenenopropylene-dene rubber. For example, see UK Patent Application No. 2005276 or US Patent No. 3,886,233. A polymer composition having the following properties is obtained.

However, these graft copolymers have rather poor flow properties, resulting in slow processing speeds and problems associated with mold filling, particularly when the article is complex.

Compared to polymer mixtures, the manufacturing process for graft copolymers is much more complex. A comparative example in West German Patent No. 2235052 (publication) includes a polymer composition consisting of 7 parts by weight of styrene noacronitrile copolymer, 27 parts by weight of chlorinated polyethylene, and 5 parts by weight of ethylenenopropylene/norbornene terpolymer. is listed.

As can be seen from this specification, this polymer composition lacks impact resistance and tensile strength. The object of the present invention is to provide impact-resistant polymer compositions which do not have the above-mentioned drawbacks. The polymer composition of the present invention comprises 'a' styrene and/or derivatives of styrene 10-90
50-95 parts by weight of one or more polymers obtained by polymerization of a mixture of 90-1% by weight of acrylonitrile and/or methacrylonitrile "and {b
} (b-1) one or more rubbers selected from ethylene/propylene and ethylene/propylene nitrogen rubber as a highly saturated rubber; and ■-2) a chlorine content of at least 1% by weight and a DSC crystallinity of at least 10 %, chlorinated polyethylene with a glass transition temperature of -1500 or higher5
5 parts by weight.

Surprisingly, the polymer compositions described above, which do not contain graft copolymers but contain certain chlorinated polyethylenes, have excellent flow properties and also exhibit very good impact resistance (even at low temperatures). was discovered.

According to Applicant's measurements, the flow properties of this polymer composition are comparable to those of styrene/acrylonitrile copolymers. In particular, its high impact resistance is amazing.

This is because a copolymer system of large saturated nitrile and chlorinated polyethylene, a system of this copolymer and large saturated rubber, or a polymer composition based on a system of these three components (however, chlorinated polyethylene has a high chlorine content , does not meet requirements for crystallinity and/or glass transition temperature)
This is because they do not exhibit impact resistance at all.
Another advantage of the polymer composition according to the invention is that the ratio between rubber, chlorinated polyethylene (CPE) and unsaturated nitrile can be varied within a wide range.

In other words, the stiffness of the final mixture, heating temperature (Pikaichi, HDT), impact strength, combustion characteristics, gloss, molding shrinkage,
Polymers whose properties such as fluidity and deformability can be adjusted within a wide range can be produced with great freedom, and there is no hindrance to the adjustment of each component, unlike in known products based on graft copolymers. Rubbery, highly saturated polymers, or highly saturated rubbers, are rubbers with almost no unsaturation in the main chain, ie less than 2 double bonds per 10 carbon atoms, preferably less than 1.5.

On the other hand, the rubber may also have unsaturated moieties in the side chains, which can be used, for example, for crosslinking. Examples of highly saturated rubbers include ethylene copolymer rubbers such as ethylenenopropylene rubber and EPT rubber.

Particularly suitable rubbers for use in the process of the invention are ethylene/propylene copolymers (so-called EP rubbers), ethylene/propylene copolymers copolymerized with butyl rubber and other polyunsaturated monomers (so-called EPT rubbers). or a mixture of two or more of these rubbers.

Examples of the polyunsaturated monomers include hexadiene-1.4
, dicyclobentadiene, tricyclobentadiene, 5
-vinylnorbornene-2,5-ethylidenenorbornene-2,5-methylenenorbornene-2,5-(2
-probenyl)norbornene-2,5-(5-hexenyl)-norbornene-2,4,718,9-tetrahydro-indene and isobropylidenetetrahydro-indene. Since vulcanization of the polymer composition is not essential, the use of polyunsaturated monomers is not necessary.
Therefore, from an economic point of view, polymer compositions include
Advantageously, propylene rubber is applied. It may be advantageous to crosslink all or part of the rubber. This can be done in the usual way. For example, peroxides or chemically modified rubbers may be applied. Chlorinated polyethylenes or mixtures of two or more chlorinated polyethylenes suitable for application to the polymer compositions of the invention are, as is well known, chlorinated polyethylene in the gas phase, solution or suspension. You can get it by converting it into

In this regard, for example, Dutch patent application no. 73117
Please see No. 8bi and Publication No. 7701599. In the process according to the invention, it is advantageous to start from high density polystyrene. That is, it is preferable to use polyethylene formed using a transition metal catalyst and having a density of 935 to 965k9/. The chlorine content is between 15 and 5% by weight, especially between 15 and 3
% by weight of chlorinated polyethylene is preferred. moreover,
The crystallinity of chlorinated polyethylene was measured using a differential scanning calorimeter (DS).
It is preferably 15% or more, especially 15 to 40% (second heating curve) measured in C).

The degree of crystallinity is determined as follows.

First, sample 5 to 11,500 in a differential scanning calorimeter.
and then cooled to 11,500 ℃ at a cooling rate of 5℃/min.
After cooling to 115,000 °C again at a rate of 5 °C min/min
Heat to. The heat of fusion is measured during this reheating. The degree of crystallinity is calculated using the following formula. Measured value of heat of fusion (J/Crystallinity (%) = 100% Theoretical heat of fusion value of crystallinity (J
The x100% glass transition temperature of ' should be -15oo or higher.

The upper limit is not very important. In fact, the upper limit of the glass transition temperature of chlorinated polyethylene is determined by the conditions imposed in terms of crystallinity and chlorine content, and this upper limit is about 110°. Here, the glass transition temperature is 0.2
Torsion damping meter with a frequency of 153 days and a heating rate of 1 °C/min.
It should be understood that this refers to the temperature at which the loss modulus G' measured at ) reaches a maximum, and around which the storage modulus G' transitions from a value specific to the glass state to a value specific to the rubber state. However, it should be noted here that chlorinated polyethylene mostly has two transition temperatures.

One transition temperature is generally around -12000,
The nature of the chlorinated polyethylene is irrelevant. The other transition temperature is higher and depends on how the chlorinated polyethylene is formed. It is the latter transition temperature that is generally referred to in the literature as the glass transition temperature of chlorinated polyethylene. Therefore, in this specification as well, the latter temperature will be referred to as the glass transition temperature of chlorinated polyethylene. By choosing a unique combination of chlorine content, DSC crystallinity, and glass transition temperature, chlorinated polyethylene, together with certain proportions of copolymer and rubber, gives the polymer surprisingly high impact resistance and , provides excellent elastic modulus and fluidity. It is therefore essential to choose the chlorination conditions such that a relatively large amount of crystalline polyethylene remains. In particular, this can be achieved when carried out at relatively low temperatures. In this way, the chlorine molecules can be distributed in a unique manner in the polymer molecules, which in itself means a relatively high glass transition temperature. Despite the high glass transition temperature, the polymer compositions of the present invention can be used at low temperatures (-12
It is surprising that the material exhibits excellent impact resistance even at temperatures as low as 0oo). In particular, Dutch Patent Publication No. 7311780 describes that chlorinated polyethylene having such a unique chlorine atom is generally hard and brittle. The formation of the unsaturated nitrile copolymer can be carried out either continuously or batchwise, and various known methods such as emulsion polymerization, suspension polymerization, solution polymerization and copolymerization, and combinations thereof are suitable.

Various acrylonitrile-based copolymers or derivatives thereof can be used as the copolymer.

Examples of copolymers that can be used are styrene/acrylonitrile copolymer, Q-methylstyrene/acrylonitrile copolymer, styrene or Q-methylstyrene/acrylonitrile/maleic anhydride turbolimer, styrene/Q
- Methystyrene/acrylonitrile terpolymers, copolymers of acrylonitrile and halogenated styrene, or mixtures of two or more of these polymers.

According to the invention, the weight ratio of chlorinated polyethylene to rubber is between 1:20 and 20:1.

Within this range, a polymer composition can be obtained that exhibits particularly excellent impact resistance even at low temperatures (-20 OO). The weight ratio of chlorinated polyethylene and highly saturated rubber is 1:4 and 4:
1, various properties are optimized.

The polymer compositions of the present invention can be made by known methods from a variety of starting materials applying commonly available methods.

Depending on the form of the starting material (powder, lump, liquid), various methods can be applied as is or in combination; for example, an impeller mixer, a Banbury mixer, a mixing extruder, etc. can be used. Since impact resistant polymer compositions are primarily sold in granular form, the polymer composition is generally ground by an extruder after mixing the starting materials.

This mixing can also be carried out in an extruder. The polymer composition of the present invention comprises {a} styrene noacrylonitrile copolymer and/or Q-methylstyrene/acrylonitrile copolymer 50
~95% by weight, (b-1) 2.5 to 25% by weight of ethylenenopropylene rubber or ethylenenopropylene rubber, (b-2) 2.5 to 25% by weight of chlorinated polyethylene {c} Additive 0 Preferably, it comprises from 1 to 1% by weight.

The polymer composition may contain conventional additives such as antioxidants, antistatic agents, lubricants, fillers, colorants, pigments, UV stabilizers, and bactericidal agents.

The polymer compositions of the present invention are particularly suitable for use in applications where stringent requirements are imposed on mechanical and physical properties such as impact resistance, stiffness, etc.

This composition is particularly suitable for applications requiring UV resistance in addition to these properties. The polymer compositions of the present invention have many uses, for example a large number of impact resistant products can be made from them.

Examples of these items include pipes, bottles, furniture, car dashboards, electrical and household cabinets and housings, shoe heels, caravans, skis,
And there are surfboards. The invention will now be described with reference to the accompanying drawings.

Specifically, Figures 1-3 are photomicrographs taken with a "scanning" electron microscope showing three different polymer compositions.
Samples were made by crushing molded sheets in liquid nitrogen. After this, the fractured surface was coated with a gold film (200A). The samples prepared in this way were examined with a scanning electron microscope and then photographed. (×1800). It can be seen from the attached photograph that only by using a very specific chlorinated polyethylene, a homogeneous and therefore properly impact resistant polymer composition can be obtained.

When compared with the polymer composition in Figure 1, it can be seen that the addition of chlorinated polyethylene actually improves the morphology of the composition, which is also evident from the impact resistance values. These improvements are not directly related to the improvements obtained by the addition of specific chlorinated polyethylene as used in the present invention.The present invention will be explained below with reference to a number of examples, but the present invention is not limited to these. Example 11 This example shows that the viscosity of an acrylonitrile copolymer can be significantly increased even with just the combination of ethylene/propylene rubber (EPT) and chlorinated polyethylene.

A copolymer of acrylonitrile and styrene was used as the nitrile copolymer.

Its nitrogen content is 6.9%, and its viscosity is 0.64'.
It was evening (125 oo and 0.1 oi of acetone 100 on the desk). The EPT rubber used had an ethylene content of 74% by weight, an ethylidene/norbornene content of 1.85% by weight, and a Hoekstra plasticity of 53. The chlorine content of the chlorinated polyethylene used was 27.5% by weight, the DSC crystallinity was 24%, and the glass transition temperature was -2°C. This chlorinated polyethylene was obtained by vapor phase chlorination of high density polyethylene. Using a laboratory roller mill, the mixture was mixed for 8 minutes at 1180 qo, during which time 0.
The composition was made by adding 25% by weight of stabilizer (lr chick noxl076).

The mechanical properties of the formed sheets were measured. Izod values (notched) were determined according to ASTM D256 and bending tests were performed according to ASTM D790. Table 1 shows the results of this example. This table includes the example number, the weight of the styrene noacrylonitrile copolymer (SAN), EPT and chlorinated polyethylene (parts by weight in the polymer composition),
Impact resistance (Izod, 1230C, KJ/), flexural modulus (N') and flexural strength (N') are listed. Table 1 Composition (parts by weight) Iso-bending elasticity Bending rate at 23°C From this example, the presence of chlorinated polyethylene and EPT is essential in order to have a sufficiently large flexural modulus and strength as well as excellent impact resistance. It turns out that.

Example Phantom to XW In this example, compositions were made according to Example M, but using chlorinated polyethylenes that were the same in chlorine content but different in DSC crystallinity and glass transition temperature.

Compositions Xm and XW were tested for impact resistance at low temperatures. The results of this example are shown in Table 2, which includes the example number, the chlorine content (wt%) of CPE, and the crystallinity (%).
), glass transition temperature (00), impact resistance at 12yo (in KJ'), flexural modulus (in N'), bending strength (N
/rail), impact strength (KJ'〆) at 0°C, -1000 and -20o0, and HDT (unannealed) (°C) are listed.

From this example, if the chlorine content is the same, what is essential for the polymer composition is the degree of crystallinity and the glass transition temperature.

The impact resistance of the polymer composition according to the present invention is even at -2000 C. The composition at 230 C.
It has become clear that it is suitable for those of the skin. Table 2 Examples X Legs - XX Skin This example relates to a composition according to Example Melon.

However, the chlorine content of the applied chlorinated polyethylene was different. The results are summarized in Table 3, which includes example number, chlorine content (wt%), crystallinity (%), glass transition temperature (00), impact resistance (IZO - 23℃,
KJ') and flexural modulus (N') are listed.

Table 3 ×Not measured This example relates to compositions according to Example Dish, K and X.

However, the ratio of EPT rubber/chlorinated polyethylene was changed. The results are shown in Table 4, which includes the example number, SAN
, amount of EPT and CPE (parts by weight), impact resistance (Wizot 12300, KJ') and flexural modulus (N')
List.

For comparison, the table includes Example V, value, D, K, m,
I'll also include blood, X, and W. Table 4 Examples XXXm to XL This example relates to Examples Kari, XV and ×Gen (different chlorinated polyethylene).

Again, the EPT rubber to chlorinated polyethylene ratio was varied. The results are shown in Table 5. For comparison purposes,
Examples Yanagi, XV and XM are also listed. The items in the table are as follows. Example number, Example number describing the type of CPE, SAN, CPE and EPT (parts by weight), impact resistance (Izod, 123oo, KJ') and flexural modulus (N/Kyo). Table 5 Examples XLI to XLO
This example relates to the composition of Example X.

However, a different EPT rubber was applied. The items in Table 6 are as follows.

Example number, SAN, amount of CPE and EPT, ethylene content of EPT (wt%), hexadiene content of EPT (wt%), ethylidenenonorbornene content of EPT (wt%), Hoekstra plasticity of EPT degree, impact resistance (Izod +23oo, KJ/me), bending modulus (
N/Kyo) and bending strength (N/Fence). Example XLm and XLW This example is a composition containing copolymers of Q-methylstylstyrene (QMSAN) and acrylonitrile with different viscosity numbers (d'') (120 oo dimethylformamide 100 0.1 mol) relating to things.

Also, different chlorinated polyethylenes were applied. The results are summarized in Table 7. The items in the table are as follows.
Example number, N content of copolymer, viscosity number of copolymer,
Amount of copolymer (parts by weight), type of CPE, amount of CPE (
(parts by weight), amount of EPT (parts by weight), impact resistance (Izod, 1230C, KJ'), bending modulus (N') and bending strength (N'). Table 6 Table 7 Examples XLV/and XLW This example relates to a composition according to Example XM.

In Example XLV, a portion of EPT was made of polyvinyl chloride (DI
K-value 7) by N53726. The same applies to the chlorinated polyethylene of Example XL. This example is West German Patent No. 2235052 (published)
This can be compared with the example in the publication.

The items in Table 8 are as follows.

Example number, SAN, CPE, PCV and EPT amount (
weight part), impact resistance (Izod, 12300, KJJ
) flexural modulus (N/bar) and bending strength (N'bar). Table 8 From the above table it can be seen that the polymer composition according to the invention has much better properties than that of the West German publication.

EXAMPLE Two unstabilized impact resistant polymer compositions, XL Blood and XL Side, were tested for UV stability.

This is an Atlas theorometer type 600W using a 6500 watt lamp and a porous silicate filter.
It was done with R. The intensity was 40 mW/m at 34 m, and irradiation was performed on one side only. The temperature in the space is 34
℃, the relative temperature was 55±5%. Example XL is a graft copolymer of styrene and acrylonitrile grafted to butadiene rubber, and Example XL is a polymer composition based on Example X.

Example XL UV stability for skin (Dynstat)
Dynstat (expressed as the irradiation time at which the impact value is halved to its original value) was four times that of Example XL skin.

[Brief explanation of the drawing]

Figure 1 shows 80% by weight of styrene/acrylonitrile copolymer.
A micrograph of a polymer composition (Example B) consisting of 75% by weight of styrene/acrylonitrile copolymer and 2% by weight of ethylene/propylene diene rubber and 12% by weight of ethylene/propylene diene rubber. Micrograph of a polymer composition consisting of 12.5% by weight of chlorinated polyethylene with a crystallinity of 5% by weight and a crystallinity of 0%, a chlorine content of 28% by weight, and a glass transition temperature of -25oC, and a third
The figure shows 75% by weight of styrene/acrylonitrile copolymer.
Microscope of a polymer composition consisting of 12.5% by weight ethylene/propylene rubber and 12.5% by weight chlorinated polyethylene with a crystallinity of 24% and a glass transition temperature of -2° C. This is a photograph.Figure 1Figure 2Figure 3

Claims (1)

Claims: 1. Impact-resistant polymer compositions based on copolymers of unsaturated nitriles, highly saturated rubbers and chlorinated polyethylene, comprising: (a) styrene and/or derivatives of styrene 10-9;
50 to 95 parts by weight of one or more polymers obtained by polymerization of 0% by weight and 90 to 10% by weight of acrylonitrile and/or methacrylonitrile (b) (b-1) Ethylene/propylene rubber as a highly saturated rubber; One or more rubbers selected from ethylene/propylene/diene rubber and (
b-2) Chlorine content is at least 10% by weight, DSC crystallinity is at least 10%, and glass transition temperature is -15
An impact-resistant polymer composition characterized in that it comprises 5 to 50 parts by weight of chlorinated polyethylene at or above 10°C. 2 As a copolymer of unsaturated nitrile, styrene and/or
or the polymer composition according to claim 1, which uses a copolymer of α-methylstyrene and acrylonitrile. 3. The polymer composition according to claim 1 or 2, wherein the chlorine content of the chlorinated polyethylene is 15 to 50% by weight. 4. The polymer composition according to any one of claims 1 to 3, wherein the chlorinated polyethylene has a crystallinity of 15 to 60% as measured by DSC. 5 Claim No. 4 in which the degree of crystallinity is 15 to 40%
Polymer compositions described in . 6 The weight ratio of chlorinated polyethylene and highly saturated rubber is 1:
A polymer composition according to any one of claims 1 to 5, wherein the ratio is 20 to 20:1. 7. The polymer composition according to claim 6, wherein the weight ratio is from 1:4 to 4:1. 8 (a) Styrene/acrylonitrile copolymer and/or
or α-methylstyrene/acrylonitrile copolymer 5
0 to 95% by weight, (b-1) ethylene/propylene rubber or ethylene/propylene/diene rubber 2.5 to 25
% by weight, (b-2) 2.5 to 25% by weight of chlorinated polyethylene, and (c) 0 to 10% by weight of additives.