JPS6031527A - Polycarbonate carbamate resin - Google Patents

Abstract

PURPOSE:The titled resin excellent in chemical resistance, melt flow, transparency, mechanical properties, and heat stability and having specified structural units and a specified reduced viscosity. CONSTITUTION:A polycarbonate carbamate resin comprising (A) structural units of formula I (wherein X is a group of formula II, formula III, -O-, -S-, -SO-, or -SO2-, R<1> and R<2> are each H or a monovalent hydrocarbon group, R<3> is a bivalent hydrocarbon group, and the aromatic rings may have halogen or monovalent hydrocarbon groups) and (B) structural units of formula IV, said units being present at a ratio of 1,000:1-2:1, and having a reduced viscosity, etasp/c, as measured in a methylene chloride solution of 0.3-2dl/g. This resin is prepared by reacting an aqueous alkaline solution of a diphenol with phosgene in the presence of an organic solvent and polymerizing the produced polycarbonate oligomer with a cyclic diamine or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polycarbonate carbamate resins. Specifically, the present invention relates to a polycarbonate tocarbamate resin that has excellent properties such as chemical resistance, melt flowability, transparency, mechanical properties, and thermal stability.

As a resin with excellent transparency and mechanical properties, λ, −
Polycarbonate resins made from monobis(4t-hydroxyphenyl)furopane (bisphenol A) and phosgene color are known, but this polycarbonate does not have sufficient chemical resistance and is inferior to oils and chemicals, so it is used as an engineering plastic. There are restrictions on its uses. Further, even if a high molecular weight polycarbonate resin is selected because it has even a slightly better chemical resistance, the high molecular weight polycarbonate has poor melt flowability and is difficult to mold.

The inventors of the present invention have conducted extensive research to obtain a resin with excellent properties, particularly chemical resistance and melt flowability, and as a result, we have developed a structural unit with a constant rate of 1%! It is well known that polycarbonate carbamate resin has properties equivalent to or superior to polycarbonate resin in various properties such as excellent chemical resistance, melt flowability t-NL, transparency, mechanical property stability, etc. The present invention was completed.

That is, 1. The purpose of the present invention is to provide a resin of great industrial value, and its gist is as follows: group, R1 and R1 are hydrogen atoms or monovalent hydrocarbon groups, R” t
Indicates an ia-valent hydrocarbon group.

The aromatic nucleus may be a halogen atom or a monovalent hydrocarbon group. ), and groups represented by the general formulas -s+, -8o-, and -so-.

R1 and R1 mineral hydrogen atoms or t monovalent hydrocarbon groups,
R"i! - Divalent hydrocarbon group R4 and Rs represent the same or different types of divalent hydrocarbons, and the aromatic nucleus may be a halogen atom or a monovalent hydrocarbon group t-Tf From the structural unit represented by .), the structural unit [1]
:The ratio of structural units [...] is /θ00:/ ~2:/dewa9
, Zhaoyuan viscosity (η5p1) measured as a methylene chloride solution
0 ) is o, s ~, 2. (Polycarbonate carbamate resin with 7 dt/ll).

Hereinafter, the non-invention will be explained in detail.

The uninvented polycarbonate carbamate resin has the general formula (wherein, X has the same meaning as in the above general formula [1]*
The m L s aromatic nucleus may have a halogen atom or a heptavalent reverted hydrogen group. ) diphenols represented by

Using cyclic diamines represented by the general formula (wherein and Bl are the same meanings as in the front foot general formula [11]) and phosgene or diaryl carbonate as raw materials, interfacial polymerization method, solution polymerization method or 7′I produced by methods such as bath melt polymerization method
2 Ru.

The diphenols represented by the above general formula [amount] include bis(4t-hydroxyphenyl)methane, l, /-
Bis(couhydroxyphenyl)ethane.

Co, 2-bis(4t-hydroxyphenyl)propane (
Bisphenol A).

2-bis(gu-hydroxyphenyl)butane.

2.2-Bis(cu-hydroxyphenyl)octane, 1-bis(cou-hydroxyphenyl)phenylmethane, 2-bis(di-hydroxy-3-methylphenyl)propane.

/,/-bis(cuhydroxy-3-tert-butylphenyl)propane.

29.2-bis(g-hydroxy-3-bromophenyl)propane.

21.2-bis(cuhydroxy-3,j-dibromophenyl)propane.

2.2-bis(4t-hydroxy-3,!-dichloro7
bis(hydroxyaryl) such as
Alkanes.

/,/-bis(couhydroxyphenyl)cyclobencune.

/,/-Bis(hydroxyaryl)cycloalkas such as bis(g-hydroxyphenyl)cyclohexane 7
a,a'-dihydroxydiphenyl ether.

dihydroxy diaryl ethers such as g,v-dihydroxy-3,r-dimethylcyphelether;

〆, dihydroxydiphenyl sulfide.

dihydroxydiaryl sulfides such as terdihydroxy-31r-dimethyldiphenyl sulfide; and terdihydroxydiphenyl sulfoxide.

dihydroxydiaryl sulfoxides such as 9'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide;

4t,<r-dihydroxy-3,! Examples include dihydro-a-xydiaryl sulfo 7s such as -dimethyldi72nyl sulfone.

Further, as the cyclic diamines represented by the above general formula [h], piperazine/, comethylbiverazine, 2.
Examples include j-dimeterbibenzine and homobipe2zine.

The polycarbonate carbamate resin of the present invention is represented by the foreleg general formula [1] - Structural unit: foreleg general formula Cl)
The ratio of structural units represented by is 1000', 1 to λ;l. If the number of structural units represented by the general formula [2] is too small, the same chemical resistance will not be sufficient. On the other hand, if it is too abundant, urea bonds will be formed in the resin chain or the number of amino groups at the end of the resin will increase, resulting in a resin with poor mechanical properties and thermal stability.

Furthermore, the polycarbonate carbamate 81 resin of the present invention has a reduced viscosity (ηsp/
C) is θ, J~2. θdL/J.

Reduced viscosity is θ,? If the ratio is smaller than (l)/l, chemical resistance and mechanical properties will deteriorate. On the contrary, ko, o d
When t and Q are larger, d fusion volume hx becomes higher and molding becomes difficult.

Such a polycarbonate carbamate tree fl'II
The diphenols represented by the general formula [Yaku] and the cyclic diamines represented by the general formula [IV] are used in a 4 molar ratio of 7000=7 to 3; Polymerization may be carried out using at least an equimolar amount of phosgene or diaryl carbonate based on the total molar amount of the base diamino compound. In addition, the reduced viscosity corresponds to the degree of polymerization.
Controlled by the use of end-capping agents such as p-cresol and the like.

The polycarbonate carbamate resin of the present invention can be polymerized by an interfacial polymerization method, a solution polymerization method, or a melt polymerization method, as in the case of producing a polycarbonate resin from bisphenol A and phosge/or diaryl carbonate. It is advantageous to carry out the polymerization by an interfacial polymerization method using a caustic alkali and an organic solvent. In particular, the alkaline aqueous solution of diphenols is reacted with phosgene in the presence of an organic solvent to produce polycarbonate oligomers such as a An interfacial polymerization method in which a polymerization reaction is carried out by adding cyclic diamines or cyclic diamines and diphenols is preferred.

Examples of the caustic alkali used in this interfacial polymerization method include sodium hydroxide, potassium hydroxide, lithium hydroxide, etc., but industrially it is preferable to use sodium hydroxide.

Examples of the organic solvent include chlorinated hydrocarbons such as methylene chloride, chloroform, dichloroethane I, trichloroethane, tetrachloroethane, /E-dichloroethane, and dichlorobenzene. In addition, these and dioxane, tetrahydrofuran, acetophenone, and toluene.

Although mixtures with organic solvents such as xylene, cyclohexane, acetone, and n-heptane can also be used, methylene chloride is preferred industrially.

In addition, in this interfacial polymerization method, triethylamine and tripropylamine are used as polymerization catalysts.

It is preferable to use tertiary amines such as tributylamine and dimethylbenzylamine, and quaternary ammonium salts such as tetramethylammonium chloride, benzyltriphthylammonium chloride, and benzyltriphthylammonium chloride.

When such an interfacial polymerization method is used, it is possible to produce a polycarbonate carbamate resin gold having extremely few terminal amino groups and containing substantially no urea bonds in the resin chain. Furthermore, there is no need for heating or high temperatures, which is industrially advantageous.

Polycarbonate carbamate resins, which have fewer terminal amino groups and fewer urea bonds, are particularly valuable because they have excellent properties such as chemical resistance, mechanical properties, and thermal stability.

The polycarbonate carbamate resin of the present invention has much better chemical resistance than polycarbonate made from bisphenol A and phosgene, which has the same reduced viscosity (ekW). There is a significant difference in the time taken to melt, and they also have excellent mechanical properties 'Jt' and melt fluidity is on the same level, so their industrial value is extremely large.

The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to the following Examples unless the gist of the invention is exceeded.

In the examples, "parts" and "%" are respectively "parts by weight" and "% by weight"? show.

In addition, the analytical values and physical property measurements in the Examples are values measured according to the following methods.

(1) Structural unit [1]: Specificity of structural unit [River] After alkaline hydrolysis of the polymer, cydiamine was analyzed in situ using high-performance liquid chromatography and calculated based on this.

(The 21-terminal amino group was dinitrophenylated with nitrofluorobenzene, followed by the 0° method.

(3) Based on the urea bond infrared absorption spectrum, the characteristic absorption of the urea bond in the vicinity of itsoorm-' was determined without ;lf.

(4) Melt-in-decool the thermostable polymer (Takara Kogyo 640n,
ηBp/ after holding at 30θ℃ for 5 minutes in L203 type)
Indicated by Q.

The difference from ηθp/c of the original polymer is small, indicating excellent extreme thermal stability.

(5) Chemical resistance Injection molded products were immersed in toluene or acetone, and the time required for the surface to whiten was shown.

(6) According to heat distortion temperature jlTM D, lr, load i/J',
Measured by ttg/CI.

(7) Izotsu impact strength ASTM D2! Measured according to t.

(8) Tensile yield strength Measured according to ASTM D 6jr.

(9) Bending strength Measured according to ASTM D790.

Example/j, Bisphenol At in 1% sodium hydroxide aqueous solution
- Prepared by dissolving/3. j% bisphenol A alkaline water r8? L methylene chloride and phosgene, respectively, 3 Kg/hr, 32. To θ! ? /
hr and j, -2kl? /hr into an external water-cooled tube reactor with an inner diameter of 6 mm and a length of 24 tm to carry out an oligomerization reaction.

The reaction mixture drawn out from the tubular reactor was separated, and η8p/C having a chloroformate group at the end was 0.03/
d1/11 polycarbonate oligomer 25.6
% methylene chloride solution was obtained.

Piperazine? d part, bisphenol Agg, / part and sodium hydroxide 22. The remaining portion was dissolved in 2,000 parts of water, and under stirring, the methylene chloride solution of the above polycarbonate oligomer/θ, θθ portion and 70 parts of a 7% triethylamine aqueous solution were added thereto, and the reaction was carried out for 20 minutes. The reaction mixture is separated into ηs having a chloroformate group at the end.
26. Polycarbonate carbamate oligomer with p/c θ and tadt/Il. V% methylene chloride solution'
? ! :Obtained.

To the methylene chloride solution of this polycarbonate carbamate oligomer, under stirring, methylene chloride/jOθ parts, p-tert-butylphenol! - 3 parts, 2θO parts of a 10% aqueous sodium hydroxide solution and 10 parts of a 1% aqueous triethylamine solution were added, and a polymerization reaction was carried out for 2 hours.

Adding 20t'0 parts of methylene chloride to the polymerization reaction mixture,
Water, Q, 1M aqueous phosphorus fermentation solution, and then repeated washing with stirring and separation with water to obtain a transparent methylene chloride solution of the polymer.

Acetone was added to a methylene chloride solution of this polymer to precipitate the polymer.

The obtained tL fc polymer has η8 p/c of 0. j66
L/I.

'iN structural unit represented by the general formula [D] general formula [I
] The polycarbonate carbamate resin had a ratio of structural units represented by 10.6<1:/, and the terminal amino group was O, and no urea bond could be detected in the polymer.

☆ Thermal stability of this polycarbonate carbamate resin, 1
Illt certain properties % heat distortion temperature, isot impact strength, tensile yield strength and bending strength were as shown in Table 1 below.

Example λ 3.7 parts of piperazine, 1641.0 parts of bisphenol and 2.0 parts of sodium hydroxide. Parts Z and J were dissolved in 20θO parts of water, and 7000 parts of a methylene chloride solution of the same polycarbonate oligomer produced in Example 1 and 10 parts of a % triethylamine aqueous solution were added thereto under stirring, and the mixture was incubated for 20 minutes. η with a chloroformate foundation at the end
A -26.j% methylene chloride solution of polycarbonate carbamate oligomer with θp/c of 0 and 1 sdt/g was obtained.

To this solution of polycarbonate carbamate oligomer in methylene chloride, add chloride, methylene jθθ parts, p-tert-butylphenol g < parts, /θ% sodium hydroxide 2θθ parts and io parts of 1% triethylamine aqueous solution, and carry out the experiment. The oligomerization reaction, washing and polymer acquisition were all carried out as in Example 1.

The equated polymer has ηs p/c of 0, 4/
The ratio of dt/l/structural unit [■]: structural unit [1] is
Laminated with 2g, g:l polycarbonate carbamate tree layer.

The terminal amino group was 0, J' tteq/g polymer, and no urin 6 bond could be detected.

The physical properties of this polycarbonate carbamate resin were as shown in Table 1 below.

Example 3 Piperazine 21. ! 6.6 parts of bisphenol A and 22.9 parts of sodium hydroxide were dissolved in 200 θ parts of water, and to this was added 7000 parts of a methylene chloride solution of the same polycarbonate oligomer as prepared in Example 1 and /% triethylamine. After adding the aqueous solution and reacting for 20 minutes, the ηe p/c with a chloroformate group at the end was 0. /u
A 26.1% solution of polycarbonate carbamate oligomer with dt/11 in methane chloride was obtained.

This polycarbonate carbamate oligomer in methylene chloride solution,! 71 Press methylene chloride! 0055. ′
Add 6 parts of p-tert-butylphenol, 1 part of 10% sodium hydroxide, and 1 part of 1% aqueous triethylamine solution.

Polymerization reaction, washing, and polymer acquisition were carried out in the same manner as in Example/Taokeru.

The obtained polymer has an ηop/c of 0.17 d1/1
The ratio of 1 structural unit [l]: structural unit [grave] is 2.31:
Made of polycarbonate carbamate resin.

What about the terminal amino group? No urea bond could be detected in the μeq/I polymer.

The physical properties of the polycarbonate carbamate resin were as shown in Table 1 below. Comparative Example 1 The same procedure as for the piperazine 7, j part in the production of the polycarbonate carbamate oligomer in Example 1 was carried out. 1ηθp/c is the structural unit of Q; sj eLt/II [
A polycarbonate resin represented by 1) was produced.

The physical properties of this polycarbonate resin were as shown in Table 1 below.

Comparative Example 2 In the production of the polycarbonate oligomer of Example 1, phosgene t, 2! t″ at 9/hr!, ?V4/
'J with hr introduced and a terminal chloroformate group
An r% methylene chloride solution of a polycarbonate oligomer having ap/a of 0.02/dt/I was obtained.

30.2 parts of piperazine and sodium hydroxide
@By water/! 00 parts, and 10,001 parts of the methylene chloride solution of the polycarbonate oligomer was added thereto under stirring.
Add 1f and react for 20 minutes &-) to form a chloroformate group at the end! η8p/C is 0, /6 dL/
77 polycarbonate carbamate oligo i-2
A 6,-2% methylene chloride solution was obtained.

To the methylene solution of this polycarbonate carbamate oligomer, 0 parts of methylene chloride, p-tert-butylphenol! , j parts, io% sodium hydroxide aqueous solution 27θ parts and 1% triethylamine water marsh solution! The polymerization reaction, washing and obtaining of the polymer were carried out in the same manner as in Example 1.

The obtained polymer has +y s d/c as θ-jjeLL
/I! Structural unit [l]: Structural unit [111 ratio is /, 2
r: Reed with polycarbonate carbamate resin.

The terminal amino group was 1.2 μeq/7 in the polymer, and no urea bond was detected.

The physical properties of this polycarbonate carbamate resin were as shown in Table 1 below.

Claims (1)

[Claims] +1) A group represented by the general formula -5-1-SO-1-so3-. R1 and R2 are monovalent hydrocarbon groups spanning hydrogen atoms*
R"La represents a 21-track hydrocarbon group. The aromatic group may have a halogen atom or a monovalent hydrocarbon group t-), and the structural unit represented by the general formula % -s- , -so +, -8o, - group, R1
and R2 is a hydrogen atom or a monovalent hydrocarbon group, R8 is a divalent hydrocarbon group, R4 and R11 are the same or different types of trivalent hydrocarbon groups, and the aromatic nucleus is a halogen atom or
Even if fc, Iri, and l-valent hydrocarbon groups t-i are discarded! stomach. ), WI structural unit [1]: Structural unit […]
The ratio is 100θ:/~2:l, and the reduced viscosity (ηep/c) suppressed as a methylene chloride solution is 0.3~.
2. θdt/g polycarbonate carbamate resin mouth (2) 4Q revised claim (1) in which the terminal amino group of the polycarbonate carbamate is 5μθv'l or less resin
Polycarbonate carbamate resin described in ). (3) The polycarbonate carbamate resin according to claim 1 or 2, which contains substantially no urea bond in the polycarbonate carbamate. (4) The polycarbonate carbamate resin according to claims (1) to (3), wherein the time required for whitening of the molded article when immersed in toluene is 1 minute or more. (5) A patent claim in which the time to whitening when a molded product is immersed in acetone is 30 seconds or more.