JPS6254342B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to (1) acid halide functional materials derived from hydroxyl-containing materials and acid halides having dihalide or multihalide functionality, (2) corresponding acyllactam functional derivatives, and (3) such functional The present invention relates to a process for producing nylon block polymers and corresponding nylon block copolymers using a nylon block copolymer. Polymers containing polyamide segments and segments of another material have been previously disclosed in the art and are hereinafter referred to as "nylon block polymers." Combining polyamide segments and segments of another polymeric material makes it possible to obtain block polymers with unique combinations of properties. These properties can be altered by changing the polyamide and/or other polymeric segments in the block polymer. It has been found that such block polymers are particularly suitable for use as fibers, fabrics, films and molding resins. U.S. Pat. Nos. 4,031,164 and 4,223,112, both to Hedrick and Gabbert, disclose nylon block polymers containing nylon segments derived from lactam monomers and other polymeric blocks derived from polyols. is taught. In the nylon block polymer taught by Hedrick and Gabbert, polyacyllactam provides the linkage for the block. Molded articles having a unique combination of properties can be made from the nylon block polymers taught therein. The aforementioned US patent teaches the preparation of the block polymer by mixing together a lactam monomer, a polyol, a lactam polymerization catalyst, and a polyacyllactam. The catalytic method for imide-alcohol condensation taught by Hedrick and Gabbert in U.S. Reissue No. 30,371 may be used in the preparation of nylon block polymers. U.S. Pat. No. 3,657,385 teaches that lactam monomers are produced by anionic polymerization of lactam monomers with a catalyst-initiator system consisting of one or more certain polyarylene polyethers as initiators or activators. Block polymers made from polymers and polyarylene polyethers are disclosed. Certain polyarylene polyether initiators disclosed as useful have terminal groups selected from the various specified groups. Alternative methods for making nylon block polymers of the type taught, for example, in the aforementioned Hedrick and Gabbert US patents will be of interest to those skilled in the art and are the object of the present invention. Another object of this invention is to provide new materials useful as intermediates for making nylon block polymers. These and other objectives will become apparent from the detailed description below. According to the invention, a lactam monomer, a basic lactam polymerization catalyst and a formula

[Formula] O call

【formula】 [In the formula, Q is

where Y is _C3 - _C11 alkylene, a is an integer of 1, 2 or 3, b is an integer of 2 or more, and R is a hydrocarbon group and an ether a divalent or polyvalent group selected from bond-containing hydrocarbon groups, where Z is (1) a polyether having a minimum molecular weight of 2000 or (2) a segment of a polyester containing a polyether segment having a minimum molecular weight of about 2000. There is provided a method for preparing a nylon block polymer comprising reacting an acyllactam functional material selected from the group consisting of: and the nylon block polymer thus obtained. Also included are materials where Z is either a hydrocarbon or polysiloxane segment. Acid halide functional materials, as referred to herein, refer to hydroxyl-containing materials with two or more carboxylic acid halide groups (i.e.

[Formula] halogen group) can be prepared by reacting with an acid halide functional material containing a halogen group. The equivalent weight of acid halide groups should be maintained in excess of hydroxyl groups in the reaction mixture. In this reaction, an acid halide material is attached to a hydroxyl position in a hydroxyl-containing material through an ester bond. Hydrogen halide is produced as a by-product from the substituted hydrogen and halogen. One example of this reaction can be described as follows. In the above reaction, R'(-OH)x is a substance containing two or more hydroxyl groups,
That is, x is at least 2, preferably 2-4. This material can be a diol, triol or even a material with a higher hydroxyl content. The group R' in the hydroxyl-containing material can be a hydrocarbon group (preferably having a molecular weight of at least 100), a polyether group or a polysiloxane group. Unless otherwise specified, "molecular weight" as used herein with respect to a polymer or polymerized segment means number average molecular weight, as can be determined by methods well known in the art, such as gel phase chromatography. The "polysiloxane" group or segment referred to here has a structure

One or more repeating units of the formula (1 siloxane unit) at least 50
% by weight of groups or segments.
In the above structures for siloxane units A can be methyl or phenyl. The polysiloxane groups or segments typically have an ether group with the residue of another group, such as a lower alkyl group, such as an ethane group, where such ether group is typically a chain of repeating siloxane units. This is a group with tangled ends at the top. These other groups preferably represent up to 50% by weight of the polysiloxane groups.
It can be up to 30% by weight. Preferred R' groups are hydrocarbon groups and polyether groups. Examples of hydrocarbon groups are alkylene in the case of diols such as ethylene glycol, and macromolecules such as segments of polybutadiene which can be functionalized to contain two or more hydroxyl groups. Hydrocarbons can be given. A polyoxypropylene segment that can be functionalized to contain two or more hydroxyl groups is one example of a polyether group. Examples of hydroxyl-containing materials useful in the above reactions include, for example, ethylene glycol, propylene glycol, poly(oxybutylene) glycol, poly(oxyethylene) glycol, poly(oxypropylene) diol, poly(oxypropylene) triol, poly(oxypropylene) blocks of poly(oxypropylene) and poly(oxyethylene) functionalized with two or more hydroxyl groups; Polymers can be mentioned. The acid halide material in the reaction, i.e.

The formula contains two or more acid halide groups, ie, groups where y is 1 or more, generally 2, 3 or 4, preferably 2.
The R groups in this acid halide material are hydrocarbon groups or hydrocarbon groups containing ether linkages (typically up to 20% by weight ether oxygen). Hydrocarbon groups are preferred, with 1 to 12 carbon atoms being most preferred. Even more preferred R groups are hydrocarbon groups or ether bond-containing hydrocarbon groups that provide at least three consecutively bonded elemental atoms between any two carbonyl groups bonded to R. Examples of preferred acid halides include sebacic acid chloride and phthalic acid chloride in which the carbonyl group is attached in either the meta or para position, ie isophthaloyl chloride and terephthaloyl chloride, respectively. structure in place of the acid halide described in the reaction above.

Acid halides having the formula can be used. In the above structure, X is halogen. In yet another aspect of the teachings herein, in place of the acid halide described as useful in the above reactions, the structure

Acid halide or structure with [formula]

[expression] or

[Formula] Phosphorus or sulfur (wherein X has the above definition and R ₁ is an alkyl group, an aryl group, an aralkyl group, a halogen group, an alkyloxy group, an aryloxy group or an aralkyloxy group) containing acid halides can be used. Examples of acid halides that can be used in the reaction include adipoyl chloride, terephthaloyl chloride, trimesoyl chloride, trimellitic acid chloride, oxalyl chloride, isophthaloyl chloride, pyromellitoyl chloride, pimeloyl chloride, and glutamate. Lyl chloride, benzophenone tetracarboxylic acid chloride, oxydiacetyl chloride, oxydibenzoyl chloride, sulfallyl chloride, phosphorus oxychloride, sebacic acid chloride, azelaic acid chloride, alkyl phosphorodichloridate, aryl phosphorodichloridate and alkaline Mention may be made of alkylphosphorodichloridate, alkylphosphonodichloridate, arylphosphonodichloridate and aralkylphosphonodichloridate. The numbers indicating the amount of functional groups for the materials described herein (eg, the numbers x, y, and b above) are integers with respect to a single molecule of the material. however,
A number of such materials, particularly polymeric materials, are generally present in mixtures or compositions containing different amounts of functionalized species, with some species perhaps in higher or lower amounts than desired. .
The numbers indicating the amount of functional groups for such mixtures or compositions represent an average of the various species and therefore are not necessarily whole numbers. Essentially all hydroxyl groups in the hydroxyl-containing starting material are converted in the reaction. By providing an excess of acid halide groups over hydroxyl groups, the resulting reaction product is functionalized with acid halide groups. The reaction is preferably carried out in the presence of a non-inhibitory solvent such as cyclohexane, toluene, tetrahydrofuran or acetone to facilitate the removal of the hydrogen halide produced.
It is also possible to drive out the hydrogen halide by heat, vacuum, nitrogen sweep, etc., and proceed with the reaction in the absence of a solvent. If a solvent is used during the reaction, a basic material that acts as an acid scavenger may be used as a convenient means of removing the hydrogen halide to produce by-products that are insoluble in the solvent. Well known acid scavengers such as tertiary amines can be used.
The reaction can be carried out under essentially ambient conditions and will proceed more rapidly at higher temperatures, such as from 30° to 150°C. The exact temperature for this reaction can depend on the solvent used.
If a solvent is used, it can be removed after the reaction by distillation. Said operation results in a reaction between the hydroxyl groups of the hydroxyl-containing material and the acid halide groups of the acid halide material. Thus, the following acid halide functionalized materials can be produced.

[expression] and

[Formula] where X is a halogen, a is an integer of 1, 2 or 3, b is an integer of 2 or more, and R is selected from a hydrocarbon group and an ether bond-containing hydrocarbon group. Z is a divalent or polyvalent group consisting of (1) polyester (the polyester is not solely composed of poly(tetramethylene terephthalate) or poly(tetramethylene isophthalate)) or (2) polyester. ether,
(3) hydrocarbon or (4) polysiloxane segment. The following acid halide functionalized materials, which represent other aspects of the teachings described herein, may also be prepared according to the procedures described above.

【formula】

[expression] and

[Formula] In the formula, R ₁ is an alkyl group, an aryl group, an aralkyl group, a halogen group, an alkyloxy group, an aryloxy group or an aralkyloxy group, X and b have the above definitions, and Z is (1)
A segment of a polyester, (2) a polyether (preferably the polyether is not just a polyarylene polyether), (3) a hydrocarbon, or (4) a polysiloxane. The Z segment in the above formula (a) and formula (b) is the above (1) polyester, (2) polyether, (3)
It is a hydrocarbon or (4) polysiloxane segment. The Z segment for the reaction products represented by formula (a) and formula (b) can be the same as the R' group of the hydroxyl functional material used in the reaction. Alternatively, the Z segment can be a segment containing two or more residues of the source hydroxyl-containing material combined together with residues of the source acid halide material. With respect to the description of Z segments or R' groups herein, it is to be understood that the description of polymeric segments/groups includes oligomeric segments/groups unless the specific usage excludes such an interpretation.
It is also to be understood that these segments/groups can be linear, branched or even star structures. The Z segment, which is a segment of polyester, can be derived from the reaction of an acid halide with dihalide or multihalide functionality with a hydroxyl-containing material, where the groups in the hydroxyl-containing material are joined together by the acid halide through polyester bonds. be combined. Examples of hydroxyl-containing starting materials that can be used in such reactions include, for example, ethylene glycol, propylene glycol, polycaprolactone diol and polycaprolactone polyol and polybutadiene diol. For example, acid halides such as those exemplified above may be used. Those skilled in the art will recognize the numerous types of polyester segments that can represent Z in formulas (a) and (b) above. The embodiment represented by formula (a) excludes polyester segments consisting solely of poly(tetramethylene terephthalate) or poly(tetramethylene isophthalate). It should be understood that a Z segment that is a polyester segment actually contains smaller segments that are in other categories of possible Z segments, such as hydrocarbon segments or polyether segments. As an example, a polyester segment, the Z segment, can be derived from a hydroxyl-containing material containing polyether groups and an acid halide material, where two or more polyether groups are bonded together by the acid halide material through an ether linkage. Become so. The hydroxyl-containing material may be derived from diols, triols or polyols. A specific example of such a product is the reaction product of poly(oxypropylene) triol and terephthaloyl chloride, in which the residue of terephthaloyl chloride forms a bond between two units derived from the triol. provide. Such polyester Z segments may be more particularly described as poly(ether-ester) segments, which are the preferred polyester segment type within the teachings of this invention. Similarly, other preferred polyester Z segments are those that are the reaction product of a diol or triol containing polymeric hydrocarbon units with an acid halide, where two or more of the polymeric hydrocarbon units are acid halides. become bound together by halide substances. Such an example is the reaction product of polybutadiene diol and terephthaloyl chloride, where two or more polybutadiene segments are linked together by the terephthaloyl chloride through an ether linkage. Polyester segments capable of representing Z can vary widely in size, but generally contain at least
It has a molecular weight of 500. Preferred molecular weights for these segments are about 1,000 to about 25,000. More preferred types of polyesters containing polyether segments or polymeric hydrocarbon segments generally contain these segments with a molecular weight of about 500 to about 4000. Additionally, as discussed below, the nature of nylon block copolymers made from acid halide functionalized materials in which the Z segment is a polyester is such that the polyester contains polyether segments having a minimum molecular weight of about 2000. In some cases, it shows unexpected results. Polyether segments are preferred Z segments in this invention. Such segments may be derived from hydroxyl-containing materials containing polyether segments. Examples of such preferred hydroxyl-containing materials include, for example, poly(oxyethylene) glycol, poly(oxybutylene) glycol, poly(oxypropylene)
Mention may be made of diols, poly(oxypropylene) triols and poly(oxypropylene) tetrols, and poly(oxypropylene)/poly(oxyethylene) block polymers functionalized with two or more hydroxyl groups. The polyether segments mentioned above generally have at least
500, preferably at least 1000 and more preferably at least about 2000. The preferred molecular weight is from about 1,000 to about 25,000, but from 2,000 to
25000 is more preferred. Even more preferred is a molecular weight of about 2000 to about 4000 for diol derivatives and about 3000 to about 3000 for triol derivatives.
12,000 and for tetrol derivatives from about 4,000 to about 16,000. As discussed in more detail below, in accordance with the present invention, the properties of nylon block copolymers made from acid halide functionalized materials in which the Z segment is a polyether can be greatly influenced by the molecular weight of that segment, and It has been determined that the preferred molecular weight yields unexpectedly advantageous results. Furthermore, it has been found that the minimal amount of cross-linking in the nylon block copolymer, which occurs when the composition of acid halide functional materials has an average functionality of 2 or greater, also unexpectedly results in improved properties. These features are discussed and illustrated more fully below. In embodiments represented by formula (b), the Z segment is simply a polyarylene polyether, ie, essentially of the formula [O-AR-O-AR], where AR is bonded to the ether oxygen through the aromatic carbon. benzenoid residue (mononuclear, dinuclear or polynuclear)]
Segments consisting only of units are excluded. The Z segment, which is a hydrocarbon segment, can be derived from a hydroxyl-containing material containing a hydrocarbon segment. The size of the hydrocarbon group can vary widely from low molecular weight alkylene groups to substantially higher molecular weight polymeric hydrocarbons. When Z is a low molecular weight hydrocarbon, acid halide functional materials of formulas (a) and (b) can be used to bond the nylon blocks together as described below. The resulting bonds will introduce the low molecular weight hydrocarbon as an addition block into the resulting nylon block polymer. Low molecular weight hydrocarbon (Z)
Examples of segments include _C2 - _C7 alkylene. Preferred Z segments in the present invention are polymeric hydrocarbon segments. As used herein, "polymeric hydrocarbon segment" means a hydrocarbon segment having a molecular weight of at least about 100 and containing two or more repeating units. Examples of hydroxyl-containing materials that can be used to provide the Z segment, which is a segment of a polymeric hydrocarbon, are alkylene (C ₈ and above) glycols and polybutadiene diols, polybutadiene diols, polybutadiene tetrols, and larger polyols of polybutadiene. can be given. Preferably, the polymeric hydrocarbon segment has a molecular weight of at least 500, more preferably from about 1,000 to about 25,000. Molecular weights of about 1000 to about 4000 for diol derivatives, about 3000 to about 12000 for triol derivatives, and about 4000 for tetrol derivatives.
Molecular weights of ˜about 16,000 are most preferred. The Z segment may also be a polysiloxane segment having the above definition. Such Z segments may be derived from hydroxyl-containing materials having polysiloxane segments. Examples of this type of hydroxyl-containing material include e.g.
There are polydimethylsiloxanes containing one or more hydroxyl functional groups. Polysiloxane segments generally have a molecular weight of at least 500, preferably at least 1000. More preferably such segments have a molecular weight of about 1000 to about 25000.
It is. It will be appreciated that the Z segment in the above formula may contain combinations of the polyester, polyether, hydrocarbon and polysiloxane segments described above. As mentioned above, preferred polyester segments contain polyether segments or polyhydrocarbon segments.
Also, as noted above, the polysiloxane segments defined herein typically contain groups other than siloxane units. It will be appreciated that other combinations of polyether, polyether, hydrocarbon and polysiloxane segments are possible and are equally useful as Z segments in the present invention. In formulas (a) and (b) above, X is halogen, preferably chlorine or bromine, and most preferably chlorine. The integer a in formula (a) is the structure

When [Formula] is used in the above reaction, 1 is preferred. The integer b in formulas (a) and (b) is at least 2, preferably from 2 to 20, most preferably from 2 to about 4. R in the above formula (a) is a divalent or polyvalent hydrocarbon group (valence equal to a+1) and corresponds to the R group in the acid halide starting material in the above reaction scheme. R ₁ in formula (b) is an alkyl group, an aryl group, an aralkyl group, an alkyloxy group, an aryloxy group, or an aralkyloxy group. Preferred acid halide functional materials taught in this invention have the formula (wherein, X is chlorine or bromine, and b is 2-
4 and R and Z have the above definitions. A further preferred form for acid halide functional materials, as described above, is one in which the R group has at least three consecutively bonded elemental atoms between any two carbonyl groups bonded to R. This is what we provide. Examples of such R groups include groups derived from adipoyl halide, isophthaloyl halide and terephthaloyl halide. It has been found that the acid halide functional materials taught herein are useful in making nylon block polymers. The acid halide functional materials of the present invention are reacted with lactam monomers to form acyl lactam functional materials, which can be further reacted with lactam monomers to form nylon block polymers. . For example, the formula
The acid halide functional material described in (a) is reacted with a lactam monomer containing from about 4 to about 12 carbon atoms to form the acyl lactam functional material described below.

[expression] and

【formula】 [In the formula, Q is

Formula (Y is C ₃ -C ₁₁ alkylene) and a, b, c, R and Z have the above definitions for formula (a) can be prepared. Similarly, the acid halide functional material described in formula (b) above can be reacted with a lactam monomer to form the acyl lactam functional material

【formula】

[expression] and

【formula】 [In the formula, Q is

where Y is C ₃ -C ₁₁ alkylene, and b, R ₁ and Z have the above definitions for formula (b), and R ₁
Q can also be produced. The reaction of acid halide functional materials with lactam monomers to produce acyllactam functional materials of formulas (a) and (b) is typically carried out using, for example, cyclohexane, toluene, acetone or an excess of lactam monomers. The reaction is carried out in the presence of a solvent such as a solvent and an acid scavenger to facilitate the removal of the hydrogen halide produced during the reaction. This reaction can also be carried out without the presence of a solvent. The discussion above regarding the use of solvents and reaction conditions for the reaction of hydroxyl-containing materials with acid halide functional materials applies here as well. Alternatively,
Acyl lactam functional materials contain hydroxyl-containing materials, acid halide functional materials, and lactam monomers without isolating the intermediate acid halide functional materials [formula (a) or formula (b)] produced. It can be prepared under similar conditions from the reaction mixture. Quantitative reactions in which essentially all halogens in the acid halide of formula (a) or formula (b) are replaced by lactam groups are preferred. The acyl lactam functional polymers of formulas (a) and (b) can then be further reacted with other lactam monomers to produce nylon block polymers. Additional hydroxyl-containing materials may be included in the reaction mixture, but the acyllactam groups should be present in excess of hydroxyl groups in the mixture. This hydroxyl-containing material becomes incorporated into the nylon block polymer. These substances should be intimately mixed. An antioxidant is generally included in the reaction mixture. This reaction is generally carried out in the presence of a suitable basic catalyst for anionic polymerization of lactams, preferably caprolactam magnesium bromide or caprolactam magnesium chloride. small amount of catalyst,
For example, up to 1 mole % of the lactam monomer to be polymerized is useful, but higher amounts, for example from 1 to 20 mole % or more, based on the lactam monomer, can also be used. Lactam monomers generally contain from 4 to about 12 carbon atoms, preferably from 6 to about 12 carbon atoms. Particularly preferred is caprolactam (here meant ε-caprolactam). For Q in formulas (a) and (b) the corresponding residues of such preferred lactam monomers are preferred. Relatively short reaction times, e.g. less than 10 minutes or even less than 30 seconds, and e.g.
The nylon block polymer is formed under mild conditions, such as at a temperature of from about 250°C to about 250°C, preferably from about 120°C to about 170°C. Lactams can be polymerized at acyl lactam sites and can also be inserted at ester and amide sites. In this way, the above
The nylon block polymers disclosed in the Hedrick and Gabbert US patents can be made. The rapid reaction times for producing nylon block polymers make the materials disclosed herein particularly useful in reaction injection molding and other similar applications, such as in-mold coating of substrates, spinning, etc. Molding, resin transfer molding and pultrusion are also expected. The relative amounts of lactam monomer and acyl lactam functional polymer used in the preparation of nylon block polymers by the above process can vary over a wide range depending on the desired nylon block polymer. The lactam monomer and the acyllactam functional polymer may be present in proportions of up to 99 parts by weight of either one and 1 part by weight of the other. The preferred amount is about 60 to about 60
% by weight lactam monomer and from about 10 to about 40% by weight
is an acyllactam functional polymer. However, to produce an elastomeric block polymer, approximately
From 40 to about 70 weight percent acyllactam functional polymer can be used. Under typical reaction conditions, polymerization is essentially quantitative. That is, essentially all of the lactam and acyllactam functional polymers are incorporated into the nylon block polymer. In the production of nylon block polymers, it is desirable to carry out the polymerization reaction in the presence of one or more other materials commonly incorporated into nylon block polymers. Such substances include, for example, fillers, plasticizers, flame retardants, stabilizers, fibrous reinforcing agents such as asbestos and glass fibres,
Examples include dyes and pigments. Such materials may be incorporated into formula (a), formula (b) or materials of formula (a) and formula (b) or other materials taught herein. The invention will now be explained in more detail by way of example. These examples are merely illustrative and should not be construed as limiting the scope of the invention, which includes various other variations. All parts, percentages, ratios, etc. are by weight unless otherwise specified. Example 1 A. Preparation of Acid Halide Functional Material A solution of 48.2 g (0.049 equivalents) of "Pluracol" GP-3030 (polyoxypropylene triol, molecular weight approximately 3000) in 40 c.c. of toluene was refluxed to produce essentially All water was removed azeotropically.
The mixture was cooled to room temperature and to it was added 9.45 g (0.103 equivalents) of crude adipoyl chloride. The solution was heated to reflux. Hydrogen chloride gas was rapidly evolved during reflux. The mixture was refluxed for 1 hour. This reaction occurs at the hydroxyl position of the polyoxypropylene triol, which is functionalized with adipoyl chloride to form a tri(acid chloride).
A functional derivative was produced. B. Preparation of Acyllactam Functional Material To the reaction product prepared in A above was added 169 ml of dry molten caprolactam. The mixture was refluxed. The reflux pot temperature rose to 185°C. Hydrogen chloride evolution occurred at a reasonable rate. The progress of the reaction was checked by periodically measuring the residual acidity.
After refluxing for 1.5 hours at 185°C, the acidity was 0.077 milliequivalents/gram (meq/gm). The solution was cooled and left overnight. Yet another toluene 45
ml and the solution was again refluxed at 140° pot temperature. After another 2 hours of reflux (total reflux time is
3.5 hours), titrated with 0.1N sodium hydroxide to the end point of phenolphthalein, and the acidity was
It was 0.042meq/gm. After refluxing for an additional 3.5 hours, the acidity did not change. This reaction occurred by replacing the chlorine atom in the product prepared in A above with a caprolactam group to produce a tri(acyllactam) functional derivative. C. Production of nylon block polymer Add 11.8 g of the reaction product produced in step B above.
Added another Pluracol GP-3030. The toluene was vacuum distilled and 25 c.c. of caprolactam was removed by distillation. The resulting solution was cooled to 75° C. and 84 ml of 0.4 molar bromomagnesium caprolactam (in caprolactam) was injected under vacuum. The mixture was stirred vigorously for 20 seconds, the vacuum was replaced with nitrogen, and the mixture was poured into a Teflon-lined mold at 130°C. After an additional 2 minutes, the polymer was removed from the mold and cut into coupons for physical testing. The resulting polymer contains approximately 20% poly(oxypropylene) and has the following properties (Examples 29-
Tensile strength 5960 (psi), 41 MPa Tensile elongation 30% Tear strength 1280 (pli), 224×10 ³ N/m Bending modulus 157000 (psi), 1082.5 MPa Izot It was a nylon block copolymer with a notch impact strength of 6.6 (foot-pounds/inch) and 352 J/m. The following polyols and acid halides were used in the preparation of additional acid halide functional polymers, acyllactam functional polymers, and nylon block polymers.

[Table] Table B Acid Halide Name Terephthaloyl chloride TERE Adipoyl chloride ADIP Isophthaloyl chloride ISOP ISOP/TERE mixture (50/50% by weight)
ISO/TER Oxydibenzoyl chloride OBC Phenylphosphonyl chloride PPC Sulfuryl chloride SC Phosphorus chloride POC Oxalyl chloride OXA Example 2 Preparation of acid halide functional substance 96.0 g in 237 ml of cyclohexane
A solution of Niax 11-34 (0.02 mol) was dried by removing 27 ml of water azeotrope during a 30 minute reflux period. Cool this solution to 21°C and add 12.18
g (0.06 mol) of terephthaloyl chloride (TERE) was added with stirring. A solution of 6.08 g (0.06 mol) triethylamine in 20 ml cyclohexane was added over 5 minutes. Temperatures start from 21℃
The temperature rose to 26°C and a white precipitate formed. The solution was heated to reflux, which was immediately cooled to 10°C and passed through Celite. Removal of the solvent under vacuum at 80°C yielded 102.48g of yellow syrup. Its IR spectrum is 1745cm ^-1 respectively
and 1800 cm ⁻¹ and no hydroxyl absorption, indicating the formation of the desired acid chloride functional polymer. Example 3 A Preparation of acid halide functional substance 48.0 g (0.01 mol) in 77 ml cyclohexane
The solution containing Niax11-34 was refluxed for 30 minutes.
Dry by removing 27 ml of water azeotrope. Cool this polyol solution to 50℃ and add
6.09 g (0.03 mol) of solid terephthaloyl chloride (TERE) was added with stirring. 3.04 g dry triethylamine in 20 ml cyclohexane
(0.03 mol) was added over 10 minutes. The temperature rose from 47.5℃ to 49℃. The resulting creamy slurry was stirred and heated at reflux for 30 minutes to complete the formation of the acid halide functional polymer. B. Preparation of Acyllactam Functional Material The reaction mixture from A above was cooled to 42° C. and 4.0 g (0.035 mol) of solid caprolactam was added thereto with stirring. 3.54 g (0.035 mol) of triethylamine in 20 ml of cyclohexane was added over 7 minutes. The temperature rose from 42°C to 53°C. Another 60 ml of cyclohexane was added and the mixture was heated to reflux with stirring for 30 minutes. A clear colorless liquid was obtained by cooling to 11° C. and passing through Celite. The solvent was removed under vacuum at 80° C. for 3 hours to yield 52.26 g of clear yellow syrup. The acidity of the resulting acyllactam functional polymeric material was 0.028 meq/gm. Example 4 Preparation of acyllactam functional substance 96.0 g in 227 ml cyclohexane
A solution of (0.02 mol) Niax 11-34 and 7.0 g (0.062 mol) caprolactam was dried by refluxing for 1 hour, during which time 27 ml of water azeotrope was removed. Cool this solution to 15°C and add
12.18 g (0.06 mol) of terephthaloyl chloride (TERE) was added with stirring. A solution of 12.66 g (0.125 mol) triethylamine in 40 ml cyclohexane was added over a period of 5 minutes.
The temperature rose from 15°C to 30°C and a white precipitate formed. The mixture was heated to reflux, held there for 1 hour, and continued to reflux for an additional hour.
The mixture was cooled to 10°C and passed through Celite. The solvent was removed under vacuum at 80° C. for 3 hours to give 93.93 g of amber syrup. The acidity of the resulting acyllactam functional polymeric material was 0.032 meq/gm. Examples 5-28 Further Examples 5-28 were carried out substantially according to Example 3 (A and B) or Example 4 above, except for the specified substances and their amounts used. The type and amount of material and method of preparation (Ex.3 or Ex.4) for each of Examples 5-28 are shown in Table C. Example 3
In some of the examples carried out accordingly, the reflux of step B was extended for more than 30 minutes, and in some cases up to 3 hours. Furthermore, in some of the examples carried out according to Example 3, a small amount of methanol or a small amount of anhydrous sodium carbonate was added after 30 to 60 minutes of reflux in step B to adjust the acidity of the final product. Ta. In some of the examples carried out according to Example 4, an equal amount of sodium carbonate was used in place of the methanol added during the reflux step. The acidity of the acyllactam functional material produced was about 0.028-0.3 meq/gm for each of these examples.

【table】

[Table] Examples 29-51 Preparation of Nylon Block Polymers The nylon block polymers were acyllactam-functionalized as prepared in Examples 5-28 by either hand casting polymerization (HC) or reaction injection molding polymerization (RIM). manufactured from polymers. These methods are described below. A. Hand casting of nylon block polymers (Examples 29-47) 500 with stirrer, thermocouple and nitrogen inlet
ml flask with caprolactam and Examples 5 to 28 above.
A prepolymer, an acyllactam functional polymer prepared according to one of the methods, was charged. The specific prepolymers and amounts of materials used in each of Examples 29-47 are shown in Table D. In each case,
1.5 g of "Frectol" H (Monsanto product, polymerized 1,2-dihydro-2 antioxidant,
2,4-trimethylquinoline) was added to the charge. The mixture was heated under vacuum to distill off 25 ml of caprolactam and cooled to 75°C. The catalyst solution, a solution of bromomagnesium caprolactam in caprolactam, was prepared separately. The catalyst solution was generally prepared by adding a 3 molar solution of ethylmagnesium bromide in diethyl ether to dry caprolactam followed by thorough degassing under vacuum. Catalyst solutions of various molar concentrations were prepared. For example, a 0.5 molar bromomagnesium caprolactam catalyst solution is 17 molar in diethyl ether.
ml of 3 molar ethylmagnesium bromide
It was prepared by adding 100 g of dry caprolactam and then degassing as described above. The molar concentrations of the catalyst solutions used for the specific examples are shown in Table D.
is shown. In addition, example 35 is 71g of P117B1/
Also contains 16″ crushed glass fiber, resulting in 25%
(Weight) Provided a glass reinforced nylon block polymer. A specific amount of catalyst solution was injected into the prepolymer solution prepared above under vacuum. The specific amounts of catalyst solution used for Examples 29-47 are shown in Table D. After stirring vigorously for 50 seconds, the vacuum was turned to nitrogen and the contacted mixture was poured into a Teflon-lined mold heated to 130°C. After standing in the mold for 5-15 minutes, the solid nylon block polymer that formed was removed. Polymerization of the prepolymer with caprolactam was essentially quantitative in the formation of the nylon block polymer. Specimens were cut for testing.

【table】

[Table] B Reaction injection molding of nylon block polymer (example)
48-51) 500 with stirrer, thermocouple and nitrogen inlet
ml flask with caprolactam and Example 5-
A prepolymer, an acyllactam functional polymer prepared according to 29, was charged. The specific prepolymers and amounts of materials used in the preparation of the prepolymer solutions in each of Examples 48-51 are listed in Table E.
is shown. 1.5 g of Frectol H was added to each charge. The mixture was dried by heating under vacuum to distill off 25 ml of caprolactam, then cooled to 75°C. Separately, a catalyst solution consisting of bromomagnesium caprolactam in caprolactam was prepared by adding a 3 molar solution of ethylmagnesium bromide in diethyl ether to dry caprolactam followed by thorough degassing under vacuum. For example, a 0.26 molar bromomagnesium caprolactam catalyst solution was prepared by adding 17 ml of 3 molar ethylmagnesium bromide in diethyl ether to 200 g of dry caprolactam. Catalyst solutions of various molar concentrations were used in the examples shown in Table E. Reaction injection molding was done by pumping the solution into a closed mold heated to 130°C. Equal volumes of prepolymer solution and catalyst solution were combined by a gear pump, with the exception of Example 48, where the prepolymer solution and catalyst solution were 3.4:
They were combined by the same means in a 1 volume ratio (prepolymer solution/catalyst solution). Mixing of these combined streams prior to injection into the mold was accomplished with an in-line (6 inch x 1/4 inch) Kenix static mixer. The mold was filled with the mixture and the resulting solid nylon block polymer was removed from the mold approximately 2 minutes after injection began. Polymerization of the prepolymer with caprolactam was essentially quantitative in the formation of the nylon block polymer. Specimens were cut for testing.

[Units are pounds per square inch (psi) or megapascals (MPa)]

Tear strength: ASTM D1004 [Units are pounds per linear inch]
Force (pli) or Newtons per meter (N/m)] Bending modulus: ASTM D790 [Units are pounds per square inch (psi) or megapascals (MPa)
Izot Notch Impact Strength: ASTM D256 [Units are foot-pounds per inch of notch or joules per meter (J/m)] Test results for Examples 29-51 are provided in Table F. There is. About these nylon block polymers
The tensile elongation (to failure) measured according to ASTM D1708 is generally greater than 50%;
In some cases it was over 200%. The polymer of Example 35 was reinforced with 25% (by weight) P117B1/16'' crushed glass fiber.

[Table] Examples 52-117 Examples 52-117 are acid halide functional materials or acyllactams containing either a polyether segment having a minimum molecular weight of about 2000 or a polyester segment containing a polyether segment having a minimum molecular weight of about 2000. Figure 2 shows unexpected results exhibited by nylon block copolymers made from functional materials. A. Preparation of Acyllactam Functional Materials Acid halide functional materials were prepared from the polyethers described in Table G below. The preparation of these acid halide functional materials consisted of preparing a solution of the desired polyether and terephthaloyl chloride in tetrahydrofuran. A sufficient amount of acid scavenger, triethylamine, was added to each solution to precipitate the white amine hydrochloride from each solution. The specific polyether (PE) and terephthaloyl chloride (TERE) molar amounts used for each solution are shown in Table H. Different acid halide functional materials were prepared for each specific polyether. In each case, acid halide functional materials containing polyether segments and acid halide functional materials containing polyester segments (containing polyether segments) were produced. These polyester segments were produced by combining polyether segments with terephthaloyl chloride residues. Acid halide functional materials containing polyether segments were prepared from a 2:1 molar ratio for diol derivatives and a 3:1 molar ratio for triol derivatives, whereas these materials containing polyester segments were They were prepared from a molar ratio of 4:3 and for the triol derivatives a molar ratio of 5:2. These acid halide to polyether molar ratios are listed as "AH/PE" in the table below. Batches of acyllactam functional material are produced by adding a solution of caprolactam and triethylamine (acid scavenger) in tetrahydrofuran to each solution of acid halide functional material. The molar amount of caprolactam used for each batch is shown in Table H below. Addition of the caprolactam solution to the solution of acid halide functional material took about 7 minutes. Each solution was heated to reflux at 76°C and maintained there for approximately 1 hour. The solutions were then allowed to cool and approximately 100 ml of tetrahydrofuran was added to each. Each batch was then filtered and further washed with tetrahydrofuran (approximately two 75 ml washes). Residual tetrahydrofuran was then removed under vacuum at 80°C for about 3 hours. The IR spectrum of Batch 1 did not show any hydroxyl absorption except for a strong ester carbonyl absorption and a weaker amide carbonyl absorption. This confirmed the production of acyllactam functional material.

【table】

【table】

【table】

Table B. Preparation of Nylon Block Copolymers Nylon block copolymers were prepared by reacting each batch of acyllactam functional material with caprolactam in the presence of the catalyst caprolactam magnesium bromide. The method used to bond these materials together was reaction injection molding. This technique is well known to those skilled in the art and consists of placing a stream of acyllactam functional material dissolved in caprolactam and a stream of caprolactam magnesium bromide catalyst dissolved in caprolactam directly into a heated mold. The catalyst solution was prepared by adding 1650 g of caprolactam to a 3000 ml flask equipped with a stirrer, thermocouple controlled heater, nitrogen inlet and distillation head for use in each nylon block copolymer preparation example except Examples 84 and 87. Manufactured by brewing.
The caprolactam was dried by distilling 50 g from the flask under vacuum (using an oil pump to obtain less than 1 mm vacuum) at a pot temperature of 125-130°C. The vacuum was changed to a nitrogen atmosphere and the caprolactam was cooled to 70°C. All atmospheric operations were performed under nitrogen. Once the caprolactam has been dried, a 3 molar solution of ethylmagnesium bromide in diethyl ether 120
ml was added for 10 minutes while maintaining vigorous shaking. Solution temperature was maintained at 100°C. Ethane and ether evolved were removed by degassing under vacuum (<1 mm) at 90° C. for 1 hour.
The catalyst solution was maintained at 90° C. and 200 ml was removed for use in each sample preparation. The catalyst solution produced was 0.225 molar. Except for Examples 84 and 87, prepolymer solutions were prepared by dissolving the acyllactam-functional prepolymers prepared according to Batches 1-23 above in caprolactam. 0.5 g of Frectol H antioxidant was added to each sample solution. The prepolymer solution was dried by distilling off 25 ml of caprolactam. These sample solutions were cooled to 85°C. In Example 84, a catalyst solution was prepared according to the procedure described above, except that only 225 g of caprolactam was dried by distilling off 25 g.
3 molar solution of ethylmagnesium bromide
19 ml was added to the caprolactam according to the procedure described above. The catalyst solution was then maintained at 90°C. The acyllactam functional material for Example 84 was not dissolved in caprolactam. instead,
181 grams of acyllactam functional material was injection molded to obtain 30% by weight polyether in the final nylon block copolymer. 1.5 g of Frectol H antioxidant was added to this acyllactam functional material prior to injection molding. As in Example 87, except that the catalyst was 16 ml of a 3 molar solution of ethylmagnesium bromide.
Manufactured in the same manner and quantities as 84. Again this acyllactam solution was not dissolved in caprolactam and 159 g of acyllactam functional material from batch no. 12 was used. The specific prepolymer batch numbers and amounts of prepolymer and caprolactam used to prepare the prepolymer solutions for each of Examples 52-117 are shown in Table J.

【table】

【table】

[Table] It was.
The nylon block copolymers in Examples 52-83, 86, and 88-117 were placed in a closed mold heated to 140°C with a 20.32 cm x 20.32 cm x 3.175 cm lumen.
It was made by pumping the prepolymer solution and catalyst solution at a 1 flow volume ratio. Example 84 and Example 87 are 1.52:1 and 1.52:1 respectively in similar molds.
It was made by pumping the prepolymer and catalyst solution at a flow volume ratio of 1.13:1. These combined streams were mixed in a 4 inch by 1/4 inch in-line Kenix static mixer prior to injection into the mold. Examples 52-117 were then subjected to substantially the following test operations: bending modulus;
Their impact properties and flexibility were determined following the Izot Notch Impact (these were previously described) and drive dart test operations. The driving dart test operation was performed using the “SPE Retec” by VAMatonis.
Bulletin” (November 1974),
It is 50.8 mm of specific NBC held against a 31.75 mm (11/4 inch) sample ring at a temperature of -29 °C.
(2 inches) 3.2 mm (1/8 inch) by diameter disc
It consists of driving a dart at 111.76 m/min (4,400 in/min) that is impacted against. Energy measurements are made with a Nicolet 1094 counting oscilloscope (in units of joules (J) or pounds x
inch]. The results of these tests are shown in Tables K-1 to K-4 below. These examples are of the polyether type (either diol derivatives or triol derivatives) to emphasize the effect that molecular weight has on impact properties.
They are ordered by weight percent of polyether in the nylon block copolymer and by AH/PE ratio.

【table】

【table】

【table】

【table】

[Table] As pointed out in Tables K-1 to K-4, their impact tests, i.e., the isot impact and driven dart tests of nylon block copolymers containing polyether segments or polyester segments containing polyether segments, An unexpected result is shown when the polyether segment has a minimum molecular weight of about 2000. For example 1000 each
and Examples 52-57 and 82-87, which contained polyether segments having a molecular weight of 725. They exhibited significantly lower impact properties than the remaining examples, which generally had molecular weights of about 2000 or higher. Examples 89-90 and Examples 91-93 showed better impact properties, but they were made from polyether segments derived from triols having a minimum molecular weight of about 1600, with the preferred minimum molecular weight being within about 2000. . This effect is more pronounced at polyether contents greater than 10% by weight of the nylon block copolymer, but it is likely that at such low amounts of polyether in the nylon block copolymer, the influence of the polyamide segments rather than the polyether segments is greater. This is because it is large. Furthermore, as noted in Table K, the impact test results for nylon block copolymers containing polyether segments and polyester segments with polyether segments are not as expected if these polyethers were derived from triols compared to diols. Show the results outside. See Examples 94-96 and 97-99 for triol derivatives and Examples 64-66 and 67-69 for diol derivatives. Both the triol and diol used had a molecular weight of approximately 3000. Also, as mentioned above, a minimal amount of cross-linking in the composition provides better properties. this is
The impact properties of nylon block copolymers made from PPG4025 (Examples 70-72 and Examples 73-75) were compared to those made from Thanol SF3950 (Example 76).
-78 and Examples 79-81). Tanol SF3950 was a composition with a functionality of about 2.1, thus allowing some minimal cross-linking. Examples 118-122 Examples 118-122 are R groups as described above [see formula (a)]
was prepared to demonstrate the effect of specific R groups on the impact and other properties of nylon block copolymers made from prepolymers with As mentioned above, preferred R groups are hydrocarbon groups that provide at least three consecutively bonded elemental atoms between the two carbonyl groups attached to R and hydrocarbon groups that have an ether linkage. . Acyl lactam functional materials were prepared by reacting polyether (NIAX) with various acid halides listed in Table L below. Some of the acid halides used (namely O-phthalic acid chloride and fumaric acid chloride) produced R groups providing no more than three consecutively bonded atoms between two carbonyl groups. The remaining halides forming the R group were other than those mentioned above providing three or more consecutively bonded atoms between two carbonyl groups. The resulting acid halide functional material was then reacted with caprolactam (the specific preparation of these materials is similar to the method described above) to form an acyllactam functional material. These acyllactam-functional materials are blended into caprolactam and reacted with a catalyst-caprolactam solution (prepared according to a method similar to that described above) to form a nylon block copolymer having a 20% polyether content by weight. was generated. These resulting nylon block copolymers were subjected to the driving dart test (described above) and the acetone extractables test (% weight loss after 24 hours in a Soxhlet extractor).

[Table] Rolide
As can be seen from Table L, the impact property (driving dart) of the nylon block copolymer is determined by the fact that the R group has at least 3 carbonyl groups bonded to it.
improved in providing 2 consecutively bonded atoms. See Examples 118, 119 and 121. Although the preferred embodiments of the present invention have been described above, various changes or substitutions can be made thereto without departing from the scope of the present invention. It is therefore to be understood that the invention has been described in an illustrative and not a restrictive manner.

Claims (1)

[Scope of Claims] 1. A lactam monomer, a basic lactam polymerization catalyst, and formulas [formula] and [formula] [wherein Q is [formula] (wherein Y is C ₃ - C ₁₁ alkylene) Yes, a is 1,
b is an integer of 2 or more, R is a divalent or polyvalent group selected from a hydrocarbon group and an ether bond-containing hydrocarbon group, and Z is (1) polyether, (2) polyester , (3) hydrocarbons, or (4) polysiloxane segments. 2. The method of claim 1, wherein Z is (1) a polyether having a minimum molecular weight of about 2,000; (2) a segment of a polyester containing a polyether segment having a minimum molecular weight of about 2,000. 3. The method of claim 2, wherein Z is (1) a polyether derived from a triol or (2) a segment of a polyester containing a polyether segment derived from a triol. 4. The method of claim 3, wherein Z is (1) a polyether having a minimum molecular weight of 3000 or (2) a segment of a polyester containing a polyether segment having a minimum molecular weight of about 2000. 5. The method of claim 2, wherein Z is (1) a polyether derived from tetrol or (2) a segment of a polyester containing a polyether segment derived from tetrol. 6 Z is a polyether derived from (1) a tetrol having a minimum molecular weight of 4000 or (2) a minimum molecular weight of about
6. A method according to claim 5, wherein the polyester segment contains a polyether segment derived from tetrol having a polyester content of 4000. 7 The above formula is A method according to any one of claims 2, 3, or 5. 8. The method of claim 7, wherein the group R provides three consecutively bonded elemental atoms between any two carbonyl groups bonded to R. 9. The method of claim 8, wherein the group R provides from about 4 to about 8 consecutively bonded elemental atoms between any two carbonyl groups attached to R. 10 R is adipoyl chloride, terephthaloyl chloride, trimezoyl chloride, trimellitic acid chloride, isophthaloyl chloride, pyromellitoyl chloride, pimeloyl chloride, glutaryl chloride, benzophenonetetracarboxylic acid chloride, oxydiacetyl 10. The method of claim 9, which is derived from an acid halide selected from the group consisting of chloride and oxydibenzoyl chloride. 10. The method of claim 9, wherein 11 R is derived from an acid halide selected from the group consisting of adipoyl chloride, terephthaloyl chloride, isophthaloyl chloride, sebacyl chloride, and azelaic acid chloride. 12. The method according to claim 2, wherein the average value of 12b exceeds 2. 13 The formula is 13. The method according to claim 12. 14. The method of claim 13, wherein the group R provides at least three consecutively bonded elemental atoms between any two carbonyl groups bonded to R. 15. The method of claim 14, wherein the group R provides from about 4 to about 8 consecutively bonded elemental atoms between any two carbonyl groups attached to R. 16. The method of claim 15, wherein 16 R is derived from an acid halide selected from the group consisting of adipoyl chloride, terephthaloyl chloride, isophthaloyl chloride, sebacyl chloride, and azelaic acid chloride. 17. According to any one of claims 12 or 13, wherein Z is (1) a polyether derived from a triol or (2) a segment of a polyester containing a polyether segment derived from a triol. Method described. 18. Claim No. 18 in which Z is a segment of a polyester containing (1) a polyether derived from a triol having a minimum molecular weight of about 3000 or (2) a polyether segment derived from a triol having a minimum molecular weight of about 3000. The method described in Section 3. 19. Any one of claims 12 or 13, wherein Z is (1) a polyether derived from tetrol or (2) a segment of a polyester containing a polyether segment derived from tetrol. Method described. 20 Z is a segment of a polyester containing (1) a polyether derived from tetrol having a minimum molecular weight of about 4000 or (2) a polyether segment derived from tetrol having a minimum molecular weight of about 4000 The method according to item 19. 21. Claim 7 or 2, wherein the polyether segment is comprised of poly(oxyethylene), poly(oxybutylene), poly(oxypropylene), or a block polymer of poly(oxypropylene) and poly(oxyethylene). The method described in any one of paragraphs 13. Claim 7, wherein 22 b is 2 to 4;
The method according to any one of paragraphs 13 and 21. 23. A method according to any one of claims 7, 13 or 21, wherein Q is the residue of caprolactam. 24 R provides at least three consecutively bonded elemental atoms between any two carbonyl groups bonded to R, and Z is (1) a hydrocarbon or (2) a polycarbonyl group; 2. The method of claim 1, wherein the composition is a segment of siloxane, and the composition has an average value of b of 2 or more. 25 The above formula is 25. The method according to claim 24. 26. The method of claim 25, wherein the group R is derived from an acid halide selected from the group consisting of adipoyl chloride, terephthaloyl chloride, isophthaloyl chloride, sebacic acid chloride and azelaic acid chloride. 27. A method according to any one of claims 7 or 13, carried out at a temperature of about 70<0>C to about 250<0>C. 28. The method of claim 25, which is carried out at a temperature of about 70<0>C to about 250<0>C. 29. The method of claim 27, which is carried out at a temperature of about 120<0>C to about 170<0>C. 30. The method of claim 28, which is carried out at a temperature of about 120<0>C to about 170<0>C. 31. The method according to any one of claims 27 or 29, wherein the catalyst is caprolactam magnesium bromide or caprolactam magnesium chloride. 32. The method according to any one of claims 28 or 30, wherein the catalyst is caprolactam magnesium bromide or caprolactam magnesium chloride. 33. Claims wherein the basic lactam polymerization catalyst is provided in an amount effective to substantially complete the polymerization of the lactam monomer and acyllactam functional material within 10 minutes to form a nylon block polymer. The method described in paragraph 1.