JPS60250029A - Polyester prepolymer and its production - Google Patents

Abstract

PURPOSE:To produce the titled prepolymer useful for conducting the anion block copolymerization of a lactam, by reacting an aliphatic polyester having OH groups on at least two terminals with an N-chlorocarbonyllactam. CONSTITUTION:An aliphatic polyester having OH groups on at least two terminals, of formula I [wherein R<1> is at least two hydrocarbon residues, E is an aliphatic polyester residue of formula II (wherein R<3> is a 2C or higher aliphatic residue, and n is a natural number)] or of formula III (wherein R<4> and R<5> are each a 2C or higher aliphatic residue, and m is a natural number), e.g., poly(epsilon- caprolactone), with an N-chlorocarbonyllactam of formula IV (wherein R<2> is a 1-12C aliphatic hydrocarbon residue), e.g., N-chlorocarbonylcaprolactam) to produce a polyester prepolymer of formula IV (wherein R<1>, R<2>, E, and P are each as defined above). This polymer is mixed with a lactam or an anion polymerization catalyst and fed to a step of anion block copolymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to polyester prepolymers useful in carrying out anionic block copolymerization of lactams.

More specifically, the present invention relates to a polyester prepolymer and a method for producing the same, which are useful in producing a polyester polyamide butt copolymer consisting of an aliphatic polyester part and a polyamide part by anionic polymerization of a lactam.

A method for producing a polyester polyamide block copolymer containing a polyester polymer portion and a polylactam polymer portion by anionic polymerization using an anionic polymerization catalyst is disclosed in Patent Publication No. 54-40120 and U.S. Patent No. 8,862,262. , 4,081.164, 4,0
84. It has been shown that this copolymer can be used for textile fibers, foam, furniture, automobile parts, etc. by utilizing its excellent properties. ing. In the method of the patent mentioned above, the polyester polyamide butt-length copolymer obtained is colored yellow.Since the 4° copolymer itself is colored yellow, it is not possible to obtain a colorless product. Not only is this not possible, but even if you want to color it in the desired color, you will only get a dull color.

Furthermore, the above-mentioned known inventions cannot synthesize star-shaped polyester prepolymers. That is, in these production methods, a prepolymer having an active group at the end synthesized by reacting a bifunctional acyllactam compound with a polyol compound as a chain extender and activator is used; is used as a chain extender, so when the chain extender is reacted with a star polyester having three or more hydroxy groups in one molecule, a network structure is created and the desired star polyester prepolymer is formed. Since these methods cannot be used to synthesize star-like protein copolymers with extremely high mechanical strength, they cannot be produced.

As a result of intensive research to obtain a polyester prepolymer having highly active functional groups at the terminals, the inventors discovered a polyester prepolymer having N-(oxycarbonyl)lactam groups at two or more terminals. This led to the invention.

That is, the present invention provides a polyester prepolymer represented by the general formula and a method for producing the prepolymer, which is characterized by reacting an aliphatic polyester having two or more hydroxyl groups at the terminals with N-chlorocarbonyl lactam. This is a method for producing polyester prepolymer.

According to the present invention, not only linear polyester prepolymers but also star-shaped polyester prepolymers can be synthesized, and furthermore, by using these polyester prepolymers, polyester polyamide block copolymers with extremely little coloring can be synthesized. A union is obtained.

The aliphatic polyester having hydroxyl groups at two or more terminals used in the method of the present invention is represented by the general formula (%). Aliphatic polyesters having hydroxy groups contain lactones or lactones having substituents.
It can be obtained by ring-opening polymerization with an alcohol or amino compound having a higher valence or a metal salt thereof, or by polycondensation of an acid halide of a dicarboxylic acid and a dihydric alcohol in a small excess of the dihydric alcohol.

R1 is a divalent or higher alcohol which is an initiator for ring-opening polymerization of lactone, or a residue responsible for activating an amino compound.

These are described in known publications, such as Takeo Saegusa, Ring-Opening Polymerization (II), pages 97-131 (Kagaku Doujin Publishing), P. W. Morgan, Condensation.
Polymers: ByInterfacial
and 5olution Methods, 32
5-898, (Interscience Pub
Types of aliphatic polyesters having two or more hydroxyl groups at the terminals include poly(ε-caprolactone), poly(δ-valerolactone), poly(β-propiolactone), and poly(β-propiolactone). Poly(ethylene adipate), poly(butylene acyphate), poly(ethylene sepacade), poly(butylene sepacade), or copolymers thereof, and poly(ε-caprolactone) is particularly preferred.

The hydrocarbon having two or more terminals used in the present invention preferably has a molecular weight of 500 to 20,000. If the number average molecular weight is less than 300, the final polyester polyamide copolymer will not have sufficient mechanical properties, especially impact strength, and problems will occur such as the number average molecular weight not exceeding 50,000. Undesirable.

Examples of the N-chlorocarbonyl lactam used in the method of the present invention include compounds represented by the general formula (wherein R is an aliphatic hydrocarbon residue of ct-C12), preferably L<
Examples include N-chlorocarbonylcaprolactam and N-chlorocarbonylpyrrolidinone.

N-Chlorocarbonyl lactam is generally synthesized by reacting laftim nitrogen and phosgene in the presence of a tertiary amine, followed by treatment with hydrogen chloride gas (Die Makromolekulare Chem).
ie 127.84-58 (1969)) Generally known methods such as distillation and removal of impurities using a porous adsorbent are used to purify the N-chlorocarbonyl lactam thus synthesized. However, preferably a method is used in which impurities are removed using a porous adsorbent.

The reason for this is that N-chlorocarbonyl lactam generally has a property of being decomposed by heating and is difficult to distill. For example, N-chlorocarbonylcaprolactam begins to decompose due to heating at around 107°C, so in order to avoid this decomposition while distilling, the temperature of the distillation pot should be kept below 105°C and the temperature should be 0.1 rmHIi.
The distillation must be carried out under a relatively high vacuum, making industrial implementation difficult.

Activated carbon is preferably used as the porous adsorbent used in the method of removing impurities using a porous adsorbent. These activated carbons include charcoal, wood flour, ash, coconut charcoal,
Purification of N-chlorocarbonyl lactam using activated carbon, which is manufactured from coal, char, etc. and is probably the type used for the purpose of removing turbidity, color, odor, etc. Above the melting point of carbonyl lactam 105
By adding activated carbon to the crude N-chlorocarbonyl lactam and mixing it at a temperature below 100°C, and then separating the activated carbon, or by passing the crude N-chlorocarbonyl lactam through a column packed with activated carbon. I can do it.

Reaction to obtain the polyester prepolymer of the invention,
That is, the reaction between an aliphatic polyester having two or more terminal hydroxyl groups and N-chlorocarbonyl lactam occurs as shown in the following formula.

The reason why such a polyester prepolymer can be synthesized from N-chlorocarbonyl lactam is that when comparing the reactivity of the acid chloride group of N-chlorocarbonyl lactam with the hydroxy group of the lactam group, the acid chloride group is much more reactive. This is because it is easy.

In the reaction between an aliphatic polyester having two or more hydroxy groups at the terminals and N-chlorocarbonyl lactam, the amounts of the aliphatic polyester and N-chlorocarbonyl lactam are preferably N- to 1 equivalent of hydroxy groups in the aliphatic polyester. The amount of chlorocarbonyl lactam is 0.7 equivalent or more and 1.5 equivalent or less, particularly preferably 00 g equivalent or more and 1.2 equivalent or less. If the amount of N-chlorocarbonyl lactam is less than 0.7 equivalent per equivalent of hydroxyl group in the aliphatic polyester, it is not preferable because the lactam may not be polymerized or the polymerization time will be extremely long when performing anionic polymerization of lactam. If the amount exceeds 1.5 equivalents, a large amount of lactam homopolymer will be produced during anionic polymerization of lactam, which is unfavorable in terms of physical properties.

The reaction temperature in the reaction of an aliphatic polyester having two or more terminal hydroxy groups and N-chlorocarbonyl lactam is preferably 0°C or more and 200°C or less,
Particularly preferably, the temperature is 10°C or more and 160°C or less.

If the reaction temperature is less than 0°C, the reaction rate will be significantly slow, and if it exceeds 200°C, a decomposition reaction will occur, which is undesirable.The reaction to obtain the polyester prepolymer should be carried out in the presence or absence of a solvent. It can also be carried out in the presence or absence of a dehydrochlorination agent. Examples of the solvent used in this reaction include methylene chloride, chloroform, carbon tetrachloride, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, cyclohexanone, dimethyl sulfoxide, dimethyl cellosolve, diglyme, benzene, toluene, xylene, and carbon disulfide. Examples of the dehydrochlorination agent include tertiary amines such as triethylamine, pyridine, dimethylaniline, and diethylaniline, but economically preferred is a method in which the reaction is carried out in the absence of a solvent and a dehydrochlorination agent.

Furthermore, adding an organometallic compound as a catalyst at the final stage of the reaction to obtain the polyester prepolymer is effective in completing the reaction, so the organometallic compound that may be used is preferably a lactam monometallic salt, such as caprolactam magnesium chloride, The polyester prepolymer of the present invention has compounds such as caprolactam magnesium bromide, caprolactam magnesium iodide, pyrrolidinone magnesium bromide, piperidone magnesium bromide, caprolactam sodium, caprolactam lithium, caprolactam potassium, etc., mixed with a lactam and an anionic polymerization catalyst. It is subjected to an anionic block copolymerization step. At this time, a substance other than the polyester prepolymer may be coexisting as the substance having an active functional group. For example, substances having active functional groups include compounds known as lactam anionic polymerization activators such as acyllactam compounds, isocyanate compounds, acid halide compounds, N-(alkoxycarbonyl)-lactam compounds, and two or more lactam polymerization activators. Examples include prepolymers such as polyoxyalkylene having terminal active functional groups, and by using these and polyester prepolymers, molded bodies with various physical properties can be obtained.

A specific method for copolymerizing the polyester prepolymer synthesized as described above and a lactam is to first mix the polyester prepolymer, lactam, and anionic polymerization catalyst at a temperature higher than the melting point of the lactam but as low as possible. If the temperature is below the melting point, sufficient mixing will not be possible, and if the temperature is too high, a polymerization reaction will occur during mixing, which is undesirable. Polymerization is carried out by raising the temperature of the mixture or by pouring it into a heated container or mold. 9 The polymerization temperature varies depending on the type of lactam, but is about 50 to 200 °C. For example, when ε-caprolactam is used as the lactam, the mixing temperature of the polyester prepolymer, ε-caprolactam, and anionic polymerization catalyst is 68 to 100 °C. °C is preferred, and the polymerization temperature is preferably 100 to 200 °C.

If the temperature is less than 100°C, polymerization will not occur, and if it exceeds 200°C, the coloring will become significant, which is not preferable.

The polymerization reaction is completed rapidly within about 1 hour.

In the block copolymerization in the method of the present invention, the amount of polyester prepolymer is 2 to 90% of the total of polyester prepolymer, lactam, and anionic polymerization catalyst.
% by weight, preferably 10-80% by weight, and 2% by weight
If it is less than that, the strength will decrease, which is not preferable.

The lactam used in the method of the present invention includes lactams such as pyrrolidinone, piperidone, ε-caprolactam, parerolactam, and laurolactam, with C-caprolactam being particularly preferred.

The amount of lactam is 5 to 97% by weight based on the total of polyester prepolymer, lactam, and anionic polymerization catalyst.
, preferably 15 to 89.7% by weight. The anionic polymerization catalyst used in the method of the present invention can be an anionic polymerization catalyst generally used for anionic polymerization of lactams. In general, all alkali metals or alkaline earth metals, or their hydrides, halohydrides, alkoxides, oxides,
hydroxide, amide, carbonate, alkyl metal,
It can be used as alkyl metal halides, lactam metals, lactam metal halides, etc., and as reactants of these with lactams, such as sodium hydroxide, potassium hydroxide, lithium oxide, ethylmagnesium bromide, phenylmagnesium bromide, fluorohydrogenation. Preferred examples include calcium, strontium carbonate, barium hydroxide, methyl sodium, butyl lithium, phenyl potassium, diphenyl barium, sodium amide, diethyl magnesium, magnesium methoxide, caprolactam magnesium bromide, caprolactam magnesium iidite, caprolactam sodium, and the like. The amount of the anionic polymerization catalyst is 0.1 to 10% by weight, preferably 0.3 to 6% by weight, based on the total of the polyester prepolymer, lactam, and anionic polymerization catalyst. Blow I copolymerization is virtually not completed, and 10% by weight
Exceeding this is not preferable because the strength of the resulting polyester polyamide butt-tock copolymer decreases.

The invention? The polyester polyamide butt copolymer synthesized using a noester prepolymer is used in applications that require high hardness, impact resistance, and heat resistance.
Polyester fibers, those with a large amount of polymer can be used as elastic bodies, and have many end uses, such as fibers,
It can be used for foam, automobile parts, electrical product parts, etc. The copolymer can be put into the form of a conventional molding resin (such as pellets) and then molded into various shapes by injection molding, extrusion molding or other molding methods, or the raw ingredients can be directly molded into molds. By polymerizing in a medium, it is also possible to obtain large-sized objects such as furniture and automobile parts.

It can be used for various purposes by modifying it with agents, fillers, plasticizers, stabilizers and other additives.

The present invention will be described in more detail with reference to Examples, but the present invention is not limited to the Examples. , 100f of poly-ε-caprolactone having two OH groups at the terminals (manufactured by Daicel Chemical Industries, Ltd.) of the type shown in Table 1 and N-chlorocarbonylcaprolactam in the amount shown in Table 1 were prepared. , 10 at 70°C
After reacting for an hour, the reaction was carried out at 100°C for 5 hours while reducing the pressure with a vacuum pump via an alkali removal tower. After cooling, a warnox-like polyester prepolymer was obtained with the yield shown in Table 1.

Reference Examples 1 to 3 show the results of anionic copolymerization of caprolactam using these polyester prepolymers. Table 1 shows the results of nitrogen elemental analysis of the analytical sample, which was washed 8 times with the system, separated from the methylene chloride layer, distilled to remove the methylene chloride, and dried under reduced pressure at 70°C for 48 hours. The analytical sample shown in Figure 1 was also analyzed at 90 MHz in deuterated chloroform using tetramethylsilane as a reference material.
Measurement was performed using a proton nuclear magnetic resonance apparatus (manufactured by Hitachi, Model R-40).

As a result, in all samples, δ1.2~i, 9p
The protons of H(b, c, d) of poly-ε-caprolactone are in pm, the protons of H(a) of poly- and monocaprolactone are in δ2.2-2.451)l)m, and the protons of H(a) of poly-ε-caprolactone are δ2.6-2.451)
2.751) The H(j) noproton of the terminal oxycarbonylcaprolactam group at pm is a s, 'I 6-8.
9 T) The proton of (f) of the terminal oxycarbonylcaprolactam group at pm is a 8.97-4.2
The proton of H(e) of poly-ε-caprolactone is at p pm, and the proton of H(k) bonded to the secondary carbon adjacent to the terminal oxycarbonylcaprolactam group converted to δ4.27 to 4.85 ppm is ( ethoxycarbonyl)
It almost coincided with the corresponding peak in the nuclear magnetic resonance spectrum of caprolactam.

H(a, b, c, d, e, f　, g, h, i.

j, k) was set to the position of H in the following equation.

Further, Table 1 shows the number of terminal oxycarbonyl caprolactams in the polyester prepolymer calculated from the integral value of this nuclear magnetic resonance spectrum (NMR).

Example 4 After purging a 200° round bottom flask equipped with a stirring device with nitrogen, a star-shaped poly-ε-caprolactone having eight terminal OH groups of the type shown in Table 2 (Daicel Chemical Industries, Ltd.) was prepared. company) 100g and the amount shown in Table 2 (
7) Prepare N-chlorocarbonylcaprolactam, 8
After reacting at 0°C for 6 hours, the pressure was reduced with a vacuum pump via an alkali removal tower, and the reaction was continued at 100'C for 5 hours. The results of anionic copolymerization of caprolactam using these star-like polyester prepolymers are shown in Reference Example 4. 80 g of the star-like polyester prepolymers obtained were The sample was washed eight times with a methylene chloride-water two-phase solvent system at 10°C or lower, the methylene chloride layer was separated, and the methylene chloride was distilled off, followed by drying under reduced pressure at 70°C for 48 hours to obtain a sample for analysis. Table 2 shows the results of nitrogen elemental analysis of the samples for analysis.

Further, this analytical sample was measured in deuterated chloroform using tetramethylsilane as a reference substance using a 99 MHz proton nuclear magnetic resonance apparatus (manufactured by Hitachi, Model R-40).

As a result, in all samples, δ1.2-1.9p
pm of poly-ε-caprolactone (b, c.

d) (7) Protons are J 2.2-2.45 ppm
The H(a) proton of poly-ε-caprolactone is
δ2.6 to 2.751) The proton of H(j) of the terminal oxycarbonylcaprolactam group is 28.76
~8.999m has a terminal oxycarbonylcaprolactam group H(f) (7) proton, δ8.9'7~4.
The H(e) proton of poly-ε-caprolactone is at 2 ppm, and the H(k) proton bonded to the secondary carbon adjacent to the terminal oxycarbonylcaprolactam group is at δ4.27 to 4.85 ppm. Each was observed.

Hf, j, k) almost coincided with the corresponding peak in the nuclear magnetic resonance spectrum of N-(ethoxycarbonyl)caprolactam.

H(a, b, c, d, e, f 1g, h, i.

j, k) were the same positions as in Examples 1-8.

Further, Table 2 shows the number of terminal oxycarbonylcaprolactam groups in the star-shaped polyester polymer calculated from the integral value of this nuclear magnetic resonance spectrum (NMR).

Reference Examples 1 to 4 1.5 g of caprolactam magnesium bromide and 6-
Mixed and dissolved caprolactam 86.5jF and 12 g of polyester prepolymer synthesized in Examples 1 to 4
were mixed at 70"C and poured into a mold heated to 165°C. A plate-shaped resin was obtained at the solidification time shown in Table 3, and its physical properties are shown in Table 8. Comparative Example 1 Polycaprolactone (Placcel 220, manufactured by Daicel Chemical Industries, Ltd.) in a nitrogen-substituted glass container
101 and 2.5 g of adipoyl biscaprolactam were charged and reacted at 120°C for 4 hours. Further inside 7
After adding and mixing 86.5 f of ε-caprolactam and 1 f of caprolactam magnesium bromide at 0°C, the mixture was poured into a mold heated to 165°C. As a result, a plate-shaped resin was obtained in the solidification time shown in Table 8,
Its physical properties are shown in Table 3.

Claims (1)

[Claims] (1) Polyester prepolymer represented by the general formula 1 (2) In a method for producing a polyester prepolymer represented by the general formula, an aliphatic polyester having two or more terminal hydroxy groups and N-chlorocarbonyl lactam are reacted. A method for producing a polyester prepolymer, the method comprising: