JPH03199230A - Copolymer polycarbonate diol - Google Patents

Abstract

PURPOSE:To obtain the title polymer providing polyurethane having excellent mechanical strength, wet heat resistance, low-temperature characteristics, etc., by using a mixture of specific two kinds of diols as an aliphatic diol of raw material. CONSTITUTION:(A) A compound (e.g. phosgene) requiring a dehydrochlorinating process, an alkylene carbonate, a diaryl carbonate or a dialkyl carbonate is reacted with (B) an aliphatic diol prepared by blending (i) 20-80 pts.wt. adduct of a 2,2-(4-hydroxyphenyl)propane shown by the formula (R is H or methyl; Ph is phenyl residue containing bond at the p-position; m and n are 1-3) with an alkylene oxide and (ii) 80-20 pts.wt. 1,6-hexanediol to give the objective polymer.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to polycarbonate diol compounds.

[Prior Art] Polyurethane resins are used in many fields such as foams, adhesives, elastomers, fibers, and paints, and their main raw materials are polyisocyanates and polyols.

Polyols include polyether polyols such as polypropylene glycol and polytetramethylene glycol, polyester polyols derived from dicarboxylic acids such as adipic acid and polyhydric alcohols, and polyols obtained by reacting lactones with alcohol. Polylactone polyols and the like are used, and are used for various purposes depending on the required performance.

However, since polyether polyol has ether bonds, urethane resins produced using it have the disadvantage of poor heat resistance and weather resistance.

On the other hand, since polyester polyols and polylactone polyols have ester bonds, urethane resins produced using them have the disadvantage of poor water resistance.

In order to obtain a new urethane resin that overcomes these drawbacks, it has been proposed to use a polyol having a carbonate bond in its molecular structure as a raw material.

The polycarbonate polyol that is currently most widely used, that is, the polyol that has carbonate bonds in its molecular structure, has l as shown in the following formula (11) in its molecular structure.
, has l1i-hexanediol as a basic skeleton.

1 HO (CH2)6[0CO (CH) KO OH・ ・ ・ ([1)
8n Polycarbonate diol has a 1,6-hexanediol structure in its basic skeleton, and the polyurethane resin obtained using it has a very well-balanced mechanical strength, heat resistance, moisture resistance, etc. It also has the advantage of being easily manufactured industrially.

[Problem to be improved by the invention] However, polycarbonate diol having this 1,6-hexanediol structure in its basic skeleton has a melting point of 40
C. to 50.degree. C., that is, at room temperature, it is a wax-like solid, so it is usually necessary to heat it to a liquid state using a melting tank or the like before use.

On the other hand, polyether polyols, which have excellent low-temperature properties, have the problem of lacking heat resistance. The present inventors have studied to solve these problems and develop a polycarbonate diol that can synthesize polyurethane with excellent mechanical strength and moisture and heat resistance, and as a result, they have arrived at the present invention.

[Structure of the Invention] That is, the present invention provides a polycarbonate diol obtained by reacting an aliphatic diol with one of the remaining compounds from the group consisting of alkylene carbonate, diaryl carbonate, and dialkyl carbonate, which require a dehydrochlorination step. , the aliphatic diol used is 20 to 80 parts by weight of an alkylene oxide adduct of 2,2-(4-hydroxyphenyl)propane represented by the following formula (1) (where R is hydrogen or (Methyl group, Ph is a residue of a phenyl group having a bond at the distal position, m and n are integers of 1 to 3) ■1. Consists of a mixture of 6-hexanediol at a ratio of 80 to 20 parts by weight. "Polycarbonate Diol with Characteristics."

Among the compounds that are one component of the polycarbonate diol in the present invention, compounds that require a dehydrochlorination step include phosgene and bischloroformate.

Examples of the alkylene carbonate include ethylene carbonate, 1,2-propylene carbonate, and 1,2-butylene carbonate.

Examples of diaryl carbonates include diphenyl carbonate and dinaphthyl carbonate.

Examples of the dialkyl carbonate include dimethyl carbonate and diethyl carbonate. these are,
Any of these can be reacted with a polyhydric alcohol described below to form a polycarbonate diol by a known method.

The alkylene oxide adduct of 2,2'bis(4-hydroxyphenyl)propane represented by the formula (1), which is another component of the polycarbonate diol of the present invention, is a known substance and is used as one of the polyol components of urethane. It is widely used in industry.

2. To produce an alkylene oxide adduct of 2-bis(4-hydroxyphenyl)propane, 2.2"bis(4-hydroxyphenyl)propane, sodium ethylate, caustic soda, caustic potash, amines, etc., and a basic catalyst. Alternatively, it can be obtained by charging an acid catalyst such as BF3 and a solvent into a reaction vessel, pressurizing ethylene oxide or propylene oxide into the vessel, and causing the reaction to occur while heating and stirring.

However, the amount of alkylene oxide added is 2 to 2 to 1 mole of 2゜2'bis(4-hydroxyphenyl)propane.
It is desirable to carry out the reaction so that the value of n and m is 4 moles, that is, 1 to 3. If it is lower than this, some of the phenolic hydroxyl groups of 2,2'bis(4-hydroxyphenyl)propane will remain, and the fatty acid It is not preferable to use it as a raw material for polyurethane, polyester, etc. because it has different reactivity with the primary alcoholic hydroxyl group of the group, and when the values of n and m are 5 or more, it becomes 2,2'bis(4-hydroxyphenyl)propane. The heat resistance of the alkylene oxide addition compound itself or the polyurethane obtained using the same decreases, which is not preferable.

The alkylene oxide adduct of 2,2″-bis(4-hydroxyphenyl)propane represented by the formula (1), which is a component of the polycarbonate diol of the present invention, is 20
~80 parts by weight, 80-20 parts of 1,6-hexanediol
Charge the ingredients in proportions of parts by weight and allow to react.

2. If the alkylene oxide adduct of 2'-bis-(4-hydroxyphenyl)propane is less than 20 parts by weight, the resulting polycarbonate diol has poor low-temperature properties and cannot achieve the performance aimed at by the present invention. .

Furthermore, if the alkylene oxide adduct of 2,2'-bis-(4-hydroxyphenyl)propane exceeds 80 parts by weight, the characteristics of 1,6-hexanediol and carbonate bond will be lost, and synthesis using this will lose its characteristics. Mechanical strength etc. cannot be obtained with polyurethane.

As the dialkyl carbonate used in the present invention, dimethyl carbonate and diethyl carbonate are suitable.

When the number of carbon atoms in the polyhydric alcohol is less than 3, those having side chains are not manufactured industrially.

On the other hand, even if a polycarbonate diol with a molecular weight exceeding 20 is used, an industrially excellent and preferred polycarbonate diol cannot be obtained.

As an example of the present invention, a reaction in which a dialkyl carbonate and an aliphatic diol are reacted to obtain a polycarbonate diol is expressed by the following general formula.

nR-OCO-R+ (n+1)HO-R-OH1 ↓ HO-R'(-0CO-R') -0H+2nRO
H1 [R is an alkyl group or chlorine, R- is an alkylene oxide adduct of 2,2-1bis(4-hydroxyphenyl)propane or a 1,6-hexanediol residue represented by formula (1)] At this time, The two types of diol compounds used as raw materials are randomly incorporated into molecules through carbonate bonds.

One piece 0-R-011, Mora one side 110-R”
-011, 10-Co-R1-0-(, -0-1
11 0 and -0CO-R2-0CO- 1111 00 react randomly and exist in the molecule.

By randomly bonding polyether chains through carbonate bonds, the crystallinity of the l,13-hexanediol skeleton is destroyed, and the resulting carbonate diol exhibits low-temperature properties. Because of the phenylene group contained in the alkylene oxide adduct of 2,2'-bis=(4-hydroxyphenyl)propane, it also has heat-resistant properties.

Next, (1) alkylene oxide adduct 2 of 2,2-1bis-(4-hydroxyphenyl)propane represented by formula (1).
0 to 80 parts by weight ■ 80 to 20 parts by weight of 1,6-hexanediol Describe the situation such as the reaction procedure when dialkyl carbonate is used as one of the raw materials for reacting with a mixed aliphatic diol. Explain in detail.

A catalyst commonly used in transesterification can be used in the reaction.

For example, lithium, sodium, potassium, rubidium,
Cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, cobalt,
There are metals such as germanium, tin, lead, antimony, arsenic and cerium and their alkoxides.

Examples of other suitable catalysts include alkali and alkaline earth metal carbonates, zinc borate, zinc oxide, lead silicate, lead arsenate, lead carbonate, antimony trioxide, germanium dioxide, cerium trioxide, and aluminum isopropoxide.

Particularly useful and preferred catalysts are organometallic compounds such as metal salts of organic acids such as magnesium, calcium, cerium, barium, zinc, tin, titanium, and the like.

The amount of catalyst used is o,ooot% to 1% of the total weight of starting materials.
．． 0% is appropriate. Preferably 0.001-0.2%
It is.

The reaction temperature is preferably about 80°C to 220°C.

At the beginning of the reaction, the reaction is carried out at a temperature near the boiling point of the dialkyl carbonate, and as the reaction progresses, the temperature is gradually raised to further advance the reaction.

The equipment capable of separating the produced alcohol and the raw material dialkyl carbonate is usually a reactor with a distillation column, and the reaction is carried out while refluxing the dialkyl carbonate.
The alcohol produced as the reaction progresses is distilled out.

At this time, some of the dialkyl carbonate is azeotroped and dissipated together with the distilled alcohol, so it is best to take this amount of dissipation into account when weighing and charging the raw materials.

According to the above reaction formula, the theoretical molar ratio is (n+1) moles of aliphatic diol to n moles of dialkyl carbonate, but in reality, the molar ratio of dialkyl carbonate/aliphatic diol is 1.1 to 1. It is better to triple it.

The reaction can be carried out at normal pressure, but in the latter half of the reaction it is carried out under reduced pressure, for example at 1 m+nHg to 200 mml (g,
It can accelerate the progress of the reaction.

The molecular weight of the polycarbonate diol in the present invention is
It can be adjusted by changing the reaction molar ratio between the raw material aliphatic diol and dialkyl carbonate, dialkylene carbonate, etc. That is, by adjusting n in the above formula, the molecular weight can be controlled.

In addition, the polycarbonate diol of the present invention can be hydrolyzed and the decomposition product can be analyzed by gas chromatography or NMR. Addendum 20
~80 parts by weight H(OCHCH2) mo-Ph+Ph −-0(CH
2CHO) nH(I) (1) It can be confirmed that 1,6-hexanediol is used in a combination of 80 to 20 parts by weight.

[Effects of the Invention] The urethane resin obtained using the polycarbonate diol of the present invention thus obtained as a raw material has well-balanced properties such as low-temperature properties, mechanical strength, heat resistance, and mixing resistance, and is suitable for elastomers, adhesives, It can be widely used in various industrial applications such as a binder for magnetic tape.

The present invention will be explained below with reference to Examples.

[Example-1] 770 g of dimethyl carbonate (8,5
5 mol), 740 g of 1,6-hexanediol (6,
27 mol), 2,2'-bis-(2,2'-(4-hydroxyphenyl)) obtained by adding and reacting 2 mol of ethylene oxide to 1 mol of propane.
4-Hydroxyphenyl) propane alkylene oxide adduct (Nippon Nyukazai Co., Ltd. product Newco119
00, OH value 346) 740 g (2.28 mol), 0.30 g of tetrabutyl titanate as a catalyst,
The reaction was carried out under normal pressure with boiling dimethyl carbonate, and methanol was distilled off.

The temperature of the reaction vessel gradually increased until it reached 200°C, and when almost no methanol was distilled out, a vacuum operation was started, and the unreacted material was distilled off under reduced pressure to a final volume of 20+n+al1g to obtain a reaction product. .

The obtained polycarbonate diol has an OH value of 56.2
It was a liquid substance.

[Comparative Example-1] Using the same apparatus as in Example-1, polycarbonate diol was similarly obtained using 100% 1,6 hexanediol as the diol compound.

[Application Example-1] Using the polycarbonate diol obtained in Example-1 and Comparative Example-1 as raw materials, polyurethane was synthesized under the reaction conditions shown below. A urethane film with a thickness of 150 microns was created from this polyurethane, and the physical properties were determined. was evaluated.

[Urethane melting reaction conditions (1) Blend composition Polyol 100 parts 1, 48G 8.3 parts MDI 35.6 parts Solvent (DMF) 267.3 parts Note) Polyol (Mw2000) / 1, 4 B
G/MD lNC010H-1,03 1,48G/polyol-2,0 (2> 100 parts of cooking schedule polyol, 8.3 parts of 1.48G.

144 parts of solvent was charged into a reactor and heated to 60°C.

Then, 35.6 parts of MDI was added and further heated.

Once the reactor temperature reaches 80°C, the reaction is continued for several hours. Thereafter, the temperature of the reactor is removed to 60°C.

When the temperature reached 60°C, 123.3 parts of solvent was added and the mixture was aged at that temperature.

(3) Properties of polyurethane NV (%) - 35 VIS (cp/25°C) - 60,000 to 80,000 Solvent - D MF (4) Preparation of film A polyurethane solution is coated on a release paper and 9 forced drying is performed.

Finished film thickness: 15G microns (5) Physical property measurement J ISB dumbbell punching Measuring instrument: Shimabara Autograph (blank below) 1: 300
% Modulus (kgf'/cm2) J: Tensile strength (kgf'/cm2)
/cm2) K: Elongation (%) 1 Ni-10℃, 100% modulus (kgr/CII+
2) M knee 10℃, 300% modulus (kgr/cm
2) N knee 30℃, 100% modulus (kgrlC
112) 0 knee 30℃, 300% modulus (kgr
1C112) The results obtained are shown in Table-1.

As is clear from the results in Table 1, the urethane film using the polycarbonate diol of the present invention has particularly excellent low-temperature properties.

Claims (1)

[Claims] A polycarbonate diol obtained by reacting an aliphatic diol with a compound selected from the group consisting of alkylene carbonate, diaryl carbonate, and dialkyl carbonate, which requires a dehydrochlorination step,
The aliphatic diol used is [1] The alkylene oxide adduct of 2,2-(4-hydroxyphenyl)propane represented by the following formula (I) ▲Mathematical formula, chemical formula, table, etc.▼...(I) 20 ~80 parts by weight (where R is hydrogen or a methyl group, Ph is a residue of a phenyl group having a bond at the para position, m and n are integers of 1 to 3) [2] 80 to 20 parts by weight of 1,6-hexanediol A polycarbonate diol comprising a mixture of parts by weight.