JPS5941326A - Polymer having excellent rigidity - Google Patents

Abstract

PURPOSE:To prepare the titled polymer having excellent mechanical characteristics such as rigidity, shear strength, etc. as well as high heat-resistance, by hydrolyzing a ring-opening polymer of a 5-norbornene-2-carboxylic acid ester derivative derived from cyclopentane. CONSTITUTION:The objective polymer having an intrinsic viscosity of 0.3-4, and composed of the constituent unit of formula I (R1 is H, alkyl or phenyl; R2 is H or alkyl) and the constituent unit of formula II (R3 is alkyl), wherein the amount of the unit of formula I is 90-100wt% based on the whole units and the trans-content of the double bond in the unit of formula I and unit of formula IIis >=40%, can be prepared preferably by (1) dissolving a ring-opening polymer of a 5-norbornene-2-carboxylic acid ester derivative in a polar organic solvent, (2) hydrolyzing in two steps e.g. with sodium hydroxide, and (3) neutralizing the product with an acid.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a polymer 4 having a five-membered ring and a double bond in its main chain, which has excellent mechanical properties such as rigidity and shear strength, and has a high level of heat resistance.

Currently, in the petrochemical industry, the C5 fraction with an extrusion number of 5 is hardly used after decomposition of naphtha, and only a small amount of imprene is used industrially as a raw material for synthetic rubber. Most of it is consumed as fuel1.Prior Art Among these C5 fractions, the highest content is cyclopentadiene, and this 7-clopentadiene is highly reactive, so it can be used as cyclopentene or norbornene derivatives. It is expected that it will be used extensively as a new high value-added product.

Among these, polymers produced by ring-opening polymerization using a norbornene derivative as a monomer using a metasense catalyst are of interest as novel engineering plastics.

Diels cyclopentadiene and acrylic acid in ten ν
Alder-reacted ring-opening polymers of 5-norbornene-2-carboxylic acid have the potential to become good heat-resistant engineering plastics, but due to their strong polarity, ring-opening polymerization does not occur.

Therefore, Japanese Patent Application Laid-Open No. 56-65018 discloses a method for obtaining a target ring-opening polymer of 5-norbornene-2-carboxylic compound re #f5m by ring-opening polymerization and transfer hydrolysis of a norbornene derivative as a Nisder compound. is proposed. This polymer is a resin with high rigidity and an excellent balance of impact resistance and heat resistance, but in the housing field, structural material field, etc., it is desired to improve the rigidity and heat resistance of the resin alone.

Therefore, the inventors of the present invention have developed a resin that meets the above-mentioned demands by taking the manufacturing research of the resin one step further.

(Ill Summary of the Invention (1) The structural unit (A) represented by the following monograin formula and the structural unit ω) (provided that 1 is a hydrogen atom, an argyl group, or a phenyl group, ■ζ2 is a hydrogen atom or an alkyl group, R3 is an alkyl group, and (a) a polymer that satisfies the following requirements (a) to (c): (a) has an intrinsic viscosity of 0. Must be between 3 and 4.0.

(b) The content of the 16th constituent 4i (4) is 90 to 100 weight 154% of the total constituent units.

The trans content of double bonds in (c+# component CA) and (B) must be 40% or more.

Ring-opened polymers with such a structure achieve a high level of rigidity that could not be achieved with conventional general-purpose engineering, and are particularly effective at shearing (1+f) [excellent strength and ease of mechanical work such as tapping]. Resin materials can be used.

1'lll'l Detailed Description of the Invention Polymer The polymer of the present invention is a polymer composed of J+1 units from the JIlν component (A) represented by and the 4t4 component (13) represented by In the above n1, R1 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 8, or a phenyl group, preferably a hydrogen atom or an alkyl group, and R2 is a hydrogen atom or the same as R1 or Different argyl groups are the same as or different from t R1, and in order to maintain the rigidity and moldability of these polymers, the intrinsic viscosity is 0.3 to 4.
．． (), particularly preferably 0.4 to 3. It is essential to meet (). If the intrinsic viscosity is less than 0.3, the heat resistance
Rigidity/llllI value! One-layer property is poor and ocular viscosity is 4. (
), the quality of JK will deteriorate.

Also, in the general formula 11 above, 41.
It is necessary that the phase containing (A) is 90 to 100 M% of the total structural units. If the content of the above-mentioned structural unit (2) is less than 90% by weight and 3% by weight, the level of stiffness and shear [υ1sensity] will be insufficient, and the level of heat resistance will decrease.

Furthermore, it is necessary that the trans content of double bonds in the structural units (4) and (B) be 40% or more. If the transformer type is less than 40%, heat resistance and rigidity will deteriorate.

The 5-norbornene-2-carboxylic acid ester derivative used in the present invention is generally prepared by combining cyclopentadiene and Nisdel acrylate Kg L''Z form or α-alkyl group (center acrylic acid ester visiting conductor). Synthesized by Diels-Alder reaction.

Norbornene-conductor monomers having these ester groups, such as methyl 5-norbornene-2-carboxylate, 5
-Methyl norbornene-2,2-carboxylate, Ethyl 5-norbornene-2-carboxylate, 5-norbornene-
2-Carbonist octyl etc. are further disclosed in Japanese Patent Application Laid-Open No. 1983-1977.
Ring-opening polymerization can be easily carried out using a metathesis catalyst described in Japanese Patent No. 999, etc.

As a metathesis catalyst, a tungsten or molybdenum compound is usually used as a transition metal component, and a tungsten compound is particularly preferred because of its high activity. Among these, tungsten halogen compounds are preferred. The organoaluminum component is not particularly limited, and for example, triethylaluminum, diethylaluminum monochloride, and ethylaluminum monochloride are used. As the third component, an oxygen-based ligand such as alcohol, a thiiso-based ligand such as pyridine, and a phosphorus-based ligand such as triphenylphosphine are used.

As the solvent, halogenated hydrocarbons, aromatic hydrocarbons, and halogenated aromatic hydrocarbons are used. Suitable for obtaining products with high trans content.

Atmospheric pressure E is sufficient for the polymerization pressure, and the polymerization can also be carried out under increased pressure.

Polymerization temperature (d, -2) is used in the range of 1°C to 70°C, but if the temperature is too low, the activity will drop significantly, and if the temperature is too high, the trans content will drop, making it impossible to obtain the desired product. Therefore, it is preferable to select within a range of about 0°C to 40°C.

Target Iji4 Item M with 40% or more transformer-containing stitches
In order to carry out the first coalescence, increase the amount of stiffness (medium) for the monomer, (1) keep the coalescence at a low temperature, or
Alcohol-based or nitrogen-based combinations can be used as component types (depending on the type of cap selected).

The polymer obtained by ring-opening polymerization [7] is represented by (where 1 is a hydrogen atom, an alkyl group, or a phenyl group, R2 is a hydrogen atom or an alkyl group, and R3 is an alkyl group). It is a ring-opening polymer of a 5-norbornene-2-carboxylic acid ester derivative composed of repeating units, and preferably has an intrinsic viscosity of 0.4 to 4.0.

However, since this ring-opened polymer itself is a Nisdel 1U conversion product, its heat resistance is low and it cannot be used practically as a heat-resistant resin.

Therefore, in this way, the ring-opened polymer of I44 is subjected to a hydrolysis treatment of the ester groups.

Although there are no limitations to the hydrolysis treatment, the following method is industrially disadvantageous.

Dissolution of the starting polymer The ester EW has 5-norpolyne-2-
A ring-opening polymer of a carboxylic acid ester is dissolved by using a ketone, tetrahydrofuran, dioxane, or dimethylformamide organic solvent. These organic solvents dissolve the opening polymer [7] and are compatible with water, and by using these organic solvents, the opening polymer described below can be industrially advantageously hydrolyzed (h/r). It can be performed.

The use h1 of these organic solvents depends on the type of polymer and
Although it varies depending on the viscosity, 5 to 5
It is common to add 50 hj parts. By adding this amount of seasoning, a uniform a liquid can be obtained.

After the first stage hydrolysis, 0% per mole of ester group units in the ring-opening polymer.
．． 92 to 3 moles of alkali is dissolved in 10 to 100 parts of water per 100 parts of organic solvent, and this is successively added to the polymer bath to effect hydrolysis of the ester groups.

As the arunonori used, hydroxides of alkali metals or alkaline earth metals and salts of these with weak acids are used, and among these alkalis, sodium hydroxide, which is a hydroxide of alkali metals, is particularly used. Potassium hydroxide, lithium hydroxide, and salts with weak acids such as sodium carbonate, sodium acetate, potassium acetate, and potassium carbonate are preferred.

The amount of alkali used is required to be 92 moles or more in total for the first and second hydrolysis steps per mole of ester group unit in the ring-opening polymer. The alkali may be added in its entirety in the first stage hydrolysis step, or may be added in divided amounts in the first stage and second stage. However, in the first hydrolysis step, 0.35% alkali was added to the ester group.
It is desirable to use more than mol.

If it is less than 0.35 mol, the hydrolysis rate will be low, and the ring-opened polymer will be dissolved into water for only 1r during the second-stage hydrolysis treatment.

Alkali is generally added as an aqueous solution, but there are no particular restrictions on the amount of alkali. Bye.

Although the hydrolysis temperature is arbitrary between 40 and 200°C, the hydrolysis proceeds satisfactorily at 50 to 80°C.

As anti-[C] progresses, the reaction system becomes heterogeneous as IJi ring polycycles coalesce.

When the second stage hydrolysis reaction system becomes non-uniform, water or alkaline water is added. The organic bulking agent may be added while being heated to distill it off, or it may be added directly without distilling it off.

The amount of water to be added is at least 31!1 per part of polymer.
More than just a proverb is necessary. If it is less than this, even if water or aqueous alkaline solution is added, it will not become a homogeneous solution. In a system in which 4v of organic solution has not been distilled off, the total amount of water added during the first-stage hydrolyzate decomposition must be equal to the amount of water added, etc. (Tsuji I-F).

If the hydrolysis temperature is in the same range as the first stage hydrolysis,
There is no problem with l and v.

After neutralization, the carboxylic acid salt in the opened polymer is converted into a carboxylic acid group by adding an acid, and the product is precipitated (47). An acid of 1° to 10 parts per carboxylate is sufficient, and the concentration of the acid used is not limited to 1° to obtain the product as a slurry. ,
Especially for carboxylic acid salts under high-speed stirring, acid (), 2~
(), 7 hours, preferably 4 to 0.6 hours, stir as is for about 0.5 to 3 hours, and then gradually add the remaining acid component to form a good powder.

In this neutralization reaction, if a predetermined amount of acid component is added to the system at once, neutralization is possible, but the amount of alkali remaining increases, the amount of alkali remaining is increased, the kinetics is reduced, and the coloring is difficult to analyze. -Measurement of physical properties The composition ratio of the product was determined to a constant lit value using red-tab 1-ray absorption spectroscopy.

The trans-containing properties were determined using the spectrum of the double bond region obtained by C-N MR spectroscopy.

The intrinsic viscosity (ηs/C) in tetrahydrofuran (concentration o
, ]y/ae), measured at 30°C.

-1 (fatty, notota? Mry is JIS/K
-7207-1974, Izotsu price wholesaler was JI
The three-point bending rigidity is JIS K-7203-1 for S・I(-711(1-1971 (3-ply 2mm thick test piece method))
973, respectively based on shear strength -7214
It's nationally established.

FiQ will be explained in detail in Examples below.

[Fruit Fabric Example-1] After purging the dried flask with nitrogen, 400 parts by weight of toluene was added as a solvent, and 5-norbornene was added as a monomer.
Charge 100-d+hV parts of methyl 2-carboxylate, R
The temperature was set at 15°C. After this, 2 tungsten hexachloride
．． Add 6 needles, then add 3 to tungsten hexachloride.
Two times the molar amount of diethylaluminium monochloride was added, and 24 moles of n-butanol relative to tungsten hexachloride were added, followed by an open-type reaction for 10 hours. After the polymerization reaction was completed, concentrated hydrochloric acid of 157j'j phase was added to methanol in an amount of 3 times the amount of toluene used, and the vinegar solution was added to the flask for catalytic decomposition. The ridge was subjected to reprecipitation purification twice using tetrahydrofuran as a good solvent and methanol as a poor solvent, and then dried to obtain 99 parts by weight of 71i combined product. The intrinsic viscosity of this polymer was 55. The trans content was 55%.Next, 100 parts by weight of the ring-opening polymer was charged, and 1,000 parts by weight of acetone was added thereto, the temperature was raised to 56°C, and the polymer was completely dissolved under stirring. Next, 50 parts of caustic potash is dissolved in 600 parts of water, and this is gradually added to the acetone solution of the ring-opening polymer so as not to reduce the degree of pain in the reaction system.

As ester hydrolysis progresses, the ring-opened polymer precipitates in the system.

Next, 600 'iJf'rj'i parts of water was added to the system,
The reaction temperature is kept constant and the reaction is continued for 1 hour. After adding water, it precipitates and becomes a uniform system.

Then, 94 parts of acetic acid is diluted with 17070 parts of water and added to the water bath solution of the ring-opening polymer. When the ring-opened 1iJ mixture is added to the final stage, the addition is stopped once, stirring is continued for 1 hour, and then the remaining whole ring is added, and the ring-opened 1iJ mixture becomes a white powder and precipitates. By filtering this, the desired 5-norbornene-2-carboxylic acid and methyl 5-norbornene-2-carboxylate can be released! 1 [Coalescence was obtained.

The physical property values of the product are shown in [Table 1].

[Example-2] Under the conditions of Example-1, 37 doses of caustic potash were distributed from 50 cities and 9 parts.
I was reacted in the same manner as in Example-1 except that the amount was reduced to parts by weight.

The physical property values of the product are shown in [Table 1].

[Actual h (mouth side-3)] Caustic Noda 3 6 was used instead of the caustic potash used in Example-1.
Table 1 shows the physical properties of the ester product that underwent water decomposition under the same preparation and reaction conditions as in Example 1, except for changing the content of the ester. - [Actual h1); Example-4] Actual 3i+i 5-norbornene-2-force 4 used in Example-1
1' In the reaction of methyl monomer, 5-norbornene-2
-Carbon City Octyl Monoha, Shun I, I4 L-,
The open chain polymer was removed. The product had a viscosity limit of 62 and a trans content of 50%.

Hydrolysis was carried out under the same charging conditions and reaction conditions as in Example-1.

The product values are shown in Table 1.

[Practical Example 111-5] 5-norbornene-2-carboxylic acid methyl 3-phenyl-5-norbornene-2-carboxylate monomer used in Practical Example-1 to obtain a ring-opened polymer.The product was 37 parts by weight,
The accuracy sail was 43, and the trans union was 53%.

Hydrolysis was carried out under the same feeding conditions and reaction conditions as in Example 1.

The physical properties of the product are shown in Table 1.

[Actual H11i Example-6] Among the open polymerization conditions used in Example-1, where n-butanol was changed to 2,6-lutidine, the intrinsic viscosity was 0.65 at the 87-heavy needle part, and the trans content was 74% ring-opened polymer! I was.

Example 7/i+i Hydrolysis was carried out under the same charging conditions and reaction conditions as in Example-1.

The physical properties of the product f1fil are shown in Table 1.

[Actual hAi Example-7] Among the ring-opening polymerization conditions used in Example-1, the tungsten hexachloride was changed to 2.1-t:ti, the polymerization temperature was changed to 5°C, and the reaction time was changed to 16 hours. An open aqueous polymer having an intrinsic viscosity of 1.2 and a trans content of 43% bt was obtained using 65-weight Wlf.

Hydrolysis was carried out under the same charging conditions and reaction conditions as in Example-1.

The physical properties of the product are shown in Table 1.

[Comparative vehicle traffic 1-1] Among the ring-opening polymerization conditions in Example-1, tungsten hexachloride was added to 0.33 + tungsten, aluminum alkyls were added to triethylaluminum, and bath When the medium was changed from toluene to chlorobenzene and the polymerization temperature was changed to 1 u' to 40°C, the result was 98! At the 4E ridge, 35% open ff1.m of F1.4 trans-containing coalesced into IH et al.

Actual) Blood j+1 Hydrolysis was carried out under the same preparation and reaction conditions as for J-1.

The physical property values of the product are shown in [Table 2].

[Comparative Example-2] 1 was added to the ring-opening polymerization system of Example-1 as a molecular end R1''J activator.
．． 5-hexadiene to tungsten hexachloride 5.
When 0 mol was added, the intrinsic viscosity was 0.28 at 71 mol.
, 48% ring-opening polymerization including trans was obtained.

Hydrolysis was carried out under the same charging conditions and reaction conditions as in the jyl-+ experiment.

The physical property values of the product are shown in [Table 2].

[Comparative Example-3] Rats with 1 raw potash were heated for 50 minutes under the conditions of 7 and 11-1.
Example-1 except that it was reduced from ton + j part to 30 okifubu.
The reaction was carried out in the same manner.

The physical properties of the product I:'4 are shown in [Table 2]. , (margin below)

Claims (1)

[Claims] (1) It is basically composed of 414 structural units (4) represented by the following general formula and structural units (B) represented by (
However, R1 represents a hydrogen atom, an alkyl group or a phenyl group, R2 represents a hydrogen atom or an alkyl group, and R3t,t represents an alkyl group. ), and the following hardness (a) to (c) (11b) Polymer value) The intrinsic viscosity is 0.3 to 4.0. (b) The content of the above constituent degree (A) is 9 in the total constituent units.
Must be 0 to 100%. (c) The trans content of the structural unit and the double bond in (B) is 40% or more.