TW593512B - Low emission polymer composition - Google Patents

Abstract

The invention comprises polymer compositions containing 3-hydroxypropanoxy terminated polymer that exhibit reduced levels of degradation product emissions during processing, by contacting the polymer in the molten state with a melt stable, organic nitrogen-containing stabilizing compound, such as polyamide.

Description

No. 593512 Case No. 89105927 1 年 丨 January Ⅰ Amendment V. Description of the Invention (1) Please file a claim 60 / 127,080 (filed on March 31, 1999. Related applications are cross-referenced. This application claims a temporary application) priority right. FIELD OF THE INVENTION The problem of the degree of emission of degradation products is caused by the problem of thermal degradation with low polymer degradation products, irritating chemicals, so, that is, they should be limited in the invention. Thing. The invention further relates to a method for manufacturing an emissive polymer article. Technical background Background Strict control ppm [AEL] 〇 3-hydroxypropoxy-terminated polymers are prone to cause acrolein emission. Acrolein is a method in which the content in the workplace must be less than 0. Summary of the invention Acrolein-emitting composition, while the base-terminated polymer is contacted with a low acrolein-containing object hydroxypropoxyl Seal compounds and objects. The present invention is a combination prepared by providing an indication of a hydroxypropoxy-terminated polymer comprising a compound that is fused by 3-propoxydine and a stable compound containing organic nitrogen. The present invention also includes a self-capped polymer to make a polymer a) Stabilizing the 3-body in the molten state and firing the polymer in a stable state containing organic nitrogen, b) Making the polymer from the detailed description of the invention 3-containing the improved stability solves this problem. The invention stabilizes the melt with an effective amount of 3-hydroxypropoxy which reduces the degree of emission of acrolein from the molten polymer. This method includes: melting of a terminal polymer with an effective amount to reduce acrylic acid

O: \ 63 \ 63218.ptc Page 4 593512 a_ _ Case No. 891Q5927 5. Description of the invention (2) 3-hydroxypropoxy-terminated polymer, that is, a polymerization with a terminal group structure of -0-CH2CH2CH20H It is easy to cause degradation during melting, which results in the generation and emission of acrylic acid CH2 = CHCHO.

3-Hydroxypropoxy-terminated polymers include polymers prepared from 1,3-propanediol or its chemical equivalent. 1,3-propanediol can be prepared chemically or biologically. For the purposes of this specification, 3-hydroxypropoxy-terminated polymers include, but are not limited to, 1,3-propanediol dicarboxylic acid esters, examples of which include poly (trimethylene terephthalate), poly (naphthalene dinaphthalate) Trimethylene carboxylate), poly (trimethylene isophthalate) and blends and copolymers thereof. Other dicarboxylic acids useful in 3-hydroxypropoxy-terminated polymers include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, and adipic acid , Sebacic acid and 1,1 2 _ dodecanedioic acid. Depending on the synthetic route used to prepare the polymers of the present invention, the dicarboxylic acid may be a dicarboxylic acid, or a lower-carbon dialkyl ester of a dicarboxylic acid, such as the dicarboxylic acid, diethyl molybdenum, or dipropyl acetate, Add to the polymerization process.

Copolymers that can be shared with the polymers of the present invention generally include any of the above dicarboxylic acids and glycols other than 1,3-propanediol, such as up to 30 mole% of such other glycols, based on the total moles of the glycol Prevail. These glycols include ethylene glycol, 1,4-butanediol, 1,2-propylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,5-pentanediol, 1, Long chain diols and polyols prepared from 6-hexanediol, 1,2-, 1,3- and 1,4-cyclohexanedifluorenol and diols or reaction products of polyols and alkylene oxides . When the polymer of the present invention is used in a blend, the blend polymer can be prepared from any of the diacids or glycols described above. Particularly preferred blends include poly (ethylene terephthalate) and poly (trimethylene terephthalate). These polymers have high molecular weight and are therefore commercially available. This molecular weight

O: \ 63 \ 63218.ptc Page 5 593512 Case No. 89105927 Amendment V. Description of the Invention (3) It can be characterized by the polymer having an intrinsic viscosity (IV) of at least 0 · 1 d 1 / g, this system. In the capillary The viscometer measures the flow time of a solution with a known polymer concentration and the flow time of a polymer solvent, as shown in ASTM D 2 8 5 7. 9 5. The polymers may be homopolymers or blends and copolymers containing at least 10% of one or more 3-hydroxypropoxy-terminated polymers. For example, a blend comprising 90% poly (ethylene terephthalate) and 10% poly (trimethylene terephthalate)-(containing up to 1% by weight polyfluorene polymer as a stabilizing compound) That is, within the intended scope of the present invention.

Melt-stable, organic nitrogen-containing stable compounds in intimate blends with 3-hydroxypropoxy-terminated polymers are selected from melt-stable first, second, and third amines, aliphatic or aromatic, and aliphatic Or aromatic amidine. Also included are polymers with functional groups containing polymer side chains or polymer backbones, such as polyamides, and copolymers and blends of polyamides. When polyamines are used, they may be linear or branched in the chain structure. Examples of linear polyamide include monomer polyamide, poly (caprolactam), nylon 6 and dimonomer polyamide, such as poly (hexamethylene adipate adipate), nylon 4, 6, Nylon 6,6, Nylon 6,10, Nylon 6,12, Nylon 12,12, or their copolymers and blends. Certain aromatic polyamidoamines, such as poly (p-phenylene terephthalamide) and poly (m-phenylene isophenylenediamine) can also be used. Polyamines prepared using tri-, tetra-, or polyfunctional amines, such as bis (hexamethylenetriamine) or βHMT, can also be used. To reduce the emission of acrolein from the 3-hydroxypropoxy-terminated polymer, the only requirement is that the stabilizing compound must contain nitrogen and be stable in the polymer melt. The stabilizing compound is preferably also liquid in a 3-propoxy-terminated polymer, and can be intimately mixed with the polymer. In general, compounds must have sufficient molecules

O: \ 63 \ 63218.ptc Page 6 593512 Amendment No. 89105927 Today, February 5th, the description of the invention (4) The amount of rhenium can be stabilized in the melt 3-propoxy-terminated polymer, in In this case, the liquid state of the compound will be a molten state. Stabilizing compounds must also not introduce or cause color in the polymer. The above-mentioned polyamides satisfy all these characteristics and are therefore a preferred class of stable compounds. Although not intending to be bound by any theory, it is believed that the nitrogen functionality in melt-stable, organic-nitrogen-containing stable compounds does not interact with the 3-hydroxypropoxy terminal of the polymer chain or its degradation products to prevent or discontinue The degradation pathway that produces acrolein is that it reacts with the acrolein produced at a molecular level to prevent or prevent emission. Amines (first, second, and third) react with aldehydes to produce different adducts, which have been well documented in the literature. For a review of amine-aldehyde reactions, see Rec. Chem. Prog., 29, 85-101 (1968). The composition of the present invention is melt stable and the amount of organic nitrogen-containing stabilizing compound is defined as an amount effective to reduce acrolein emission. This amount is generally less than 10% by weight, based on the amount of 3-propoxy-terminated polymer present. An amount of 1% by weight has been shown to be effective. An effective amount can range from about 0.01% to about 10% by weight. Articles of manufacture made from 3-hydroxypropoxy-terminated polymers, copolymers, and blends may include fibers (single-component, two-component, such as two-component with poly (ethylene terephthalate)) (Or multiple components), fibers, films, castings and molded parts. The manufacture of these articles generally requires that the starting polymer must be in a molten form at some stage in the manufacturing process. That is to say, it is most likely to launch at this melting stage. A composition comprising a 3-hydroxypropoxy-terminated polymer and a melt stable, organic nitrogen-containing stabilizing compound can be stabilized by a sheet or granular 3-hydroxypropoxy-terminated polymer and a solid melt, containing organic Nitrogen stable compounds are formed by mixing.

O: \ 63 \ 63218.ptc Page 7 593512 Case No. 89105927 β 丨 Year of the month Amendment V. Description of the invention (5) The resulting mixture can then be melt processed, that is, in an extruder. Forming compact Polymer mixture. Alternatively, the solution is stable and a stable compound containing organic nitrogen may be added to and mixed with the 3-hydroxypropoxy-terminated polymer melt stream. When using polyamines or copolymers of polyamines or polyamines as melt-stabilizing, organic nitrogen-containing stabilizing compounds, this material can be used with 3-hydroxypropoxy-terminated polymers before processing. Blend dry or add to the melt of the 3-hydroxypropoxy terminated polymer as a melt. Oligomers containing nitrogen functionality of melt-stable, organic nitrogen-containing stable compounds may also be incorporated into 3-propoxy-terminated polymers. 3-Solid phase solidification of propoxy-terminated oligomers can occur in the presence of stable compounds containing oligomeric or polymeric nitrogen. In all of these cases, the 3-hydroxypropoxy-terminated polymer and the stabilizing compound are in contact with each other when the former is in a molten state. All objects obtained from this melting system, such as filaments, films or molded parts, will not be accompanied by a harmful amount of acrylic acid in the surrounding atmosphere. In the following examples, the spin spinning test was performed in a spin spinning assembly containing the following: control container, spiral combination, spinning assembly-containing 105 holes of short-fiber spinneret; circulation of 39 pounds (1 7 7 kg) / hour and polymer residence time is about 5 minutes. Before adding each polymer, stop the screw and clean the control container. Prior to the spiral start, each polymer material was controlled at 160 ° C and then circulated for 30 minutes. All samples were taken 30 minutes after the spiral system stabilized. To measure acrolein, the NIOSH method NIOSH 2532 M was used. Examples Comparative Examples 1 and 2 A sample of poly (trimethylene terephthalate) polymer particles prepared by condensation of terephthalic acid bis (3-hydroxypropyl ester poly) with an intrinsic viscosity of 1.02 dl / g was introduced.

O: \ 63 \ 63218.ptc Page 8 593512 Amendment _ # 8910M97 V. Description of the invention (6) This is a spinning spinning device of 2 7 4 C. After spinning for 30 minutes, air f-sampling was performed at the spinner, 4 忖 (10.16 cm) below and 5 inches (12. 7 cm) before the yarn bundle. Sample sampling time was 5 minutes (1 litre of air per minute) and 30 minutes. The results obtained are shown in Table 1 as Comparative Examples 1 and 2, respectively. Columns 1 and 2 were spun as in Comparative Example 1, but the feed added to the melt-spinning assembly consisted of 99.9% by weight poly (trimethylene terephthalate—same batch as above) and 1% by weight. Polyamide 6 polymer (40 RV, containing 0.0 2 5% Ti〇2, from Nylmex,

Monterrey, Mexico). 15 points and 30 points of air sample data are shown in Table 1 as Examples 1 and 2, respectively. Examples 3 and 4 were spun as in Comparative Example 1 (and Example 1), but the feed to the melt spinning assembly was 95% by weight poly (trimethylene terephthalate—the same batch as above) and A physical mixture of 5 wt% commercial 6-Polymer 6 polymer (40 RV, containing 0 025% TiO, available from Nylmex, Monterrey, Mexico). The 15 and 30 air samples are shown in Table 1 as Examples 3 and 4, respectively. Table 1 Example of air sample No. Polymer temperature Nylon 6wt% Sample volume liter * Acrolein ________ (ur / r) Lingbi Je- * 45— Dagger 4 4 4 4 4 4 7 7 7 7 7 7 2 2 2 2 2 2 5 0 5 0 5 0 1 3 13 13

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O: \ 63 \ 63218.ptc Page 9 593512 _ Case No. 89105927 Θ Amended February 1, 2015_ 5. Description of the invention (7) * Air sampling speed = 1 liter / min These results show that when polyamide is incorporated into the polymerization Acrolein that occurs in the melt when it comes into contact with 3-hydroxypropoxy-terminated polymers when acrolein emission originally occurs, and when 3-hydroxypropoxy-terminated polymers are produced from a molten state The emission is reduced about 10 times. Similar results can be obtained when other melt-stable, nitrogen-containing stabilizing compounds are used instead of or in addition to polyamide.

O: \ 63 \ 63218.ptc Page 10 593512 _Case No. 89105927 Θ 丨 February_ Amendment Schematic description O: \ 63 \ 63218.ptc Page 11

Claims (1)

593512 _Case No. 89105927_Year_Day__ VI. Scope of Patent Application The stable polymer containing organic nitrogen is a polymer containing amidamine functional group. 7. The composition of claim 1 or 3, wherein the melt-stable, organic nitrogen-containing stable polymer is an amine-functional polymer. 8. The method as claimed in item 2 or 4 of the patent application, wherein the melt-stable, organic nitrogen-containing stable polymer is a polymer containing an amine functional group 9. The composition as claimed in item 1 or 3 of the patent application Wherein the melt-stable, organic nitrogen-containing stable polymer is selected from the group consisting of nylon 6, nylon 4, 6, nylon 6, 6, nylon 6, 10, nylon 6, 12, 2, nylon 1, 2, 1, 2, or A group of copolymers and blends. 10. The method according to item 2 or 4 of the scope of patent application, wherein the melt-stable, organic nitrogen-containing stable polymer is selected from the group consisting of nylon 6, nylon 4, 6, nylon 6, 6, nylon 6, 1 0, A group consisting of nylon 6,1 2, nylon 1, 2, 1, 2, or its copolymers and blends. 1 1. The composition according to item 1 or 3 of the scope of patent application, wherein the solution-stable, organic nitrogen-containing stable polymer is selected from the group consisting of poly (p-phenylene p-phenylenediamine), poly (m-- A group consisting of phenyl isophenylenediamine) and polyamine prepared from bis (hexamethylenetriamine). 12. The method according to item 2 or 4 of the scope of patent application, wherein the solution-stable, organic nitrogen-containing stable polymer is selected from poly (p-phenylene p-phenylenediamine), poly (m-phenylene A group consisting of phenylisophenylenediamine) and polyamidamine prepared from bis (hexamethylenetriamine). 1 3. A method for preparing fibers from poly (trimethylene terephthalate) or a copolymer thereof, the method comprising: O: \ 63 \ 63218-921231.ptc Page 13 593512 _Case No. 89105927_Amendment __ Sixth, the scope of patent application a) Provide (i) contains the poly (trimethylene terephthalate) polymer Or a polymer blend of a polymer, and (ii) providing a molten melt stability of 0.01 to 10% based on the poly (trimethylene terephthalate) polymer or copolymer Polyamine or polyamine stabilized polymer to reduce the emission of acrolein self-polymerized (trimethylene terephthalate) polymer or copolymer, and form (i) and (i 1) the first patent application scope A composition; and b) spinning the composition into fibers. 14. The method according to item 13 of the scope of patent application, wherein the melt-stabilized polyamine or polyamine stabilized polymer is selected from the group consisting of amine or amine containing polymer as a polymer side chain or a polymer main chain. Groups of things. 15. The method according to item 14 of the scope of patent application, wherein the melt-stabilized polyamine or polyamine stabilized polymer is a polymer containing a amine functional group. 16. The method according to item 14 of the scope of patent application, wherein the stable polymer of the melt-stabilized polyamine or polyamine is an amine-functional polymer. 1 7. The method according to item 14 of the scope of patent application, wherein the melt-stabilized polyamine or polyamine stabilized polymer is selected from the group consisting of nylon 6, nylon 4,6, nylon 6,6, and nylon 6,1 0 , Nylon 6,1 2, Nylon 1, 2, 1 2 or its copolymers and blends. 1 8. The method according to item 14 of the scope of patent application, wherein the melt-stabilized polyamine or polyamine stabilized polymer is selected from poly (p-phenylene p-phenylenediamine), poly (m- A group consisting of phenylisophenylenediamine) and polyamidoamine prepared from bis (hexamethylenetriamine). O: \ 63 \ 63218-921231.ptc Page 14