CN109943067B - Pure hydrolysis-resistant polyamide composition and preparation method thereof - Google Patents
Pure hydrolysis-resistant polyamide composition and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a pure hydrolysis-resistant polyamide composition and a preparation method thereof, wherein the pure hydrolysis-resistant polyamide composition comprises the following components in percentage by mass: 40-84.80wt% of polyamide (A), 15-60.00wt% of glass fiber, 0.10-0.50wt% of ethylene-maleic anhydride copolymer and 0.10-0.30wt% of antioxidant (A); wherein the polyamide (A) is polyhexamethylene adipamide and has terminal amino groups of more than 70mmol/kg or terminal carboxyl groups of less than 60 mmol/kg; adding polyamide and functional additives into a main feeding port of an extruder, adding glass fiber into a middle-section side feeding port, extruding and drawing by a screw, granulating and drying to obtain a pure polyamide composition with long-term heat-resistant chlorine water, and soaking the polyamide composition in hot chlorine water (Cl content is 5ppm) at 90 ℃/1000 hours to obtain the polyamide composition with the tensile strength retention rate of at least 50%.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a pure hydrolysis-resistant polyamide composition and a preparation method thereof.
Background
In the field of water pipe products and fittings, lead-free treatment is increasingly paid attention, and lead pollution can endanger the reproductive capacity, renal function and nervous system of people. Under the harm of lead exceeding of the traditional copper products, the new replacement scheme is always attracted by the attention of the industry, and high-function engineering plastics are an important direction. Compared with the traditional copper material and other metal materials for replacing the copper material, the engineering plastic has the advantages of light weight, corrosion resistance, easy manufacture and the like, and the polyamide material is the most common choice.
Tap water is generally disinfected by chlorination, so that free chlorine is present. Water pipe products used in families and public places also need to meet the use requirement of hot water, and the temperature can reach 85 ℃ or above. In the hot water state, free chlorine can accelerate corrosion of plastics, so that the product is cracked and fails prematurely, the phenomenon is called hydrolysis, and the material for water pipe products and fittings is required to have long-term hydrolysis resistance. In an attempt to improve hydrolysis resistance, it is conventional to add hydrolysis resistance or hydrophobic aids to polyamide resins. For example, chinese patent CN102311638B discloses a hydrolysis-resistant polyamide composition containing CuI, KBr and fatty acid salt type auxiliary agent, and chinese patent application CN102115593A adds a hydrophobic and oleophobic masterbatch containing fluorine copolymer on the basis of adding Cu antioxidant to improve the hydrolysis-resistant function of polyamide material. The above scheme has the disadvantages that the added alkali metal antioxidant is easy to separate out, has pollution to water and is not suitable for the field of domestic water. Chinese patent application CN105949763A discloses an environment-friendly hot water stable polyamide composition, which avoids the method of adding alkali metal antioxidant, but needs to be processed by a double-vacuum special process, and the disclosed material has a hydrolysis resistance function of only short term and is still far away from the long-term hydrolysis resistance target.
In view of the above, the prior art fails to provide a purified polyamide composition that meets the requirements for long-term exposure to hot chlorinated water, and further improvements are desired.
Disclosure of Invention
The invention aims to provide a pure polyamide composition with long-term heat-resistant chlorine water, which is environment-friendly, pollution-free and long-term hydrolysis-resistant.
It is another object of the present invention to provide a process for the preparation of said polyamide composition.
The above object of the present invention is achieved by the following technical solutions:
the pure hydrolysis-resistant polyamide composition comprises the following components in percentage by mass:
further, the polyamide composition comprises the following components in percentage by mass:
wherein the sum of the mass percentages of the combination (a) to the component (f) is 100 wt%.
The polyamide (A) is polyhexamethylene adipate (PA66), preferably polyamide 66 having more than 70mmol/kg of terminal amino groups, less than 60mmol/kg of terminal carboxyl groups, and preferably more than 80mmol/kg of terminal amino groups, less than 50mmol/kg of terminal carboxyl groups.
The content of the terminal amino group and the terminal carboxyl group can be measured by the following method: PA66 sections were dissolved in 2, 2, 2-trifluoroethanol, the amino group was titrated with a 0.02mol/L standard solution of hydrochloric acid, and then the carboxyl group was titrated after neutralizing excess hydrochloric acid with 0.02mol/L sodium hydroxide.
Calculating the terminal amino group content using formula (I):
in the formula: v1Titration of the volume of the standard titration solution consumed at the most abrupt point in the end group determination, mL;
C1-molarity, mol/L of standard titration solution;
m-mass of sample, g.
The carboxyl end group content was calculated using formula (II):
in the formula: v2-neutralizing excess hydrochloric acidConsuming the volume of NaOH standard solution, namely ml;
V3-the volume of NaOH standard solution, ml, consumed in testing the carboxyl groups;
m is the mass of the sample, g;
C2-NaOH standard solution titration molarity, mol/L.
The polyamide (B) is a mixture of one or more aliphatic long carbon chain polyamides. The long carbon chain polyamide has advantages of lower water absorption and better processing characteristics, and disadvantages of inferior initial mechanical properties and heat resistance to polyamide 66, and higher cost.
The long carbon chain polyamide refers to polyamide containing at least one monomer unit and at least 10 linearly arranged carbon atoms. The following table illustrates the abbreviations for the monomer units used to label the polyamides:
HMDA NH2-(CH2)6-NH2hexamethylene diamine
DA10 NH2-(CH2)10-NH2Decamethylenediamine
DA12 NH2-(CH2)12-NH2Dodecanediamine
ADA HOCO-(CH2)4-COOH adipic acid
DC10 HOCO-(CH2)8-COOH sebacic acid
DC12 HOCO-(CH2)10-COOH dodecanedioic acid
AA11 NH2-(CH2)10-COOH 11-aminoundecanoic acid
ADA12 NH2-(CH2)11-COOH 12-aminododecanoic acid
Examples of the polyamide resin include polyhexamethylene sebacamide (PA610), polyhexamethylene dodecanoamide (PA612), polydecamethylenesebacamide (PA1010), polydecamethylenedodecanoamide (PA1012), poly-11-aminoundecanoamide (PA11), poly-12-aminoundecanoamide (PA12) and polydecamethylenedodecanoamide (PA 1212).
PA610 is a homopolymer derived from the polymerization of HMDA and DC 10.
PA612 is a homopolymer derived from the polymerization of HMDA with DC 12.
PA1010 is a homopolymer derived from the polymerization of DA10 with DC 10.
PA1012 is a homopolymer derived from the polymerization of DA10 with DC 12.
PA11 is a homopolymer derived from the polymerization of AA 11.
PA12 is a homopolymer derived from the polymerization of ADA 12.
PA1212 is a homopolymer derived from the polymerization of DA12 with DC 12.
The mass ratio of the polyamide (B) to the polyamide (A) is 1-10:20, preferably 1-2: 4.
the glass fiber is a glass fiber with a round or irregular cross section. The cross section of the glass fiber with the special-shaped cross section can have various shapes including cocoon shapes, rectangles, ellipses, rectangles, polygons and the like, the cross section ratio of the glass fiber with the special-shaped cross section is 2-5, the short diameter of the cross section is 3-13 mu m, and the long diameter of the cross section is 10-50 mu m. The diameter of the round interface glass fiber monofilament is 5-20 μm, preferably 7-17 μm, and more preferably 9-13 μm.
The ethylene-maleic anhydride copolymer is prepared by copolymerizing ethylene and maleic anhydride in a copolymerization ratio of 1: 1, less than 22% by mass of ethylene, more than 78% by mass of maleic anhydride and a molecular weight of about 60000.
The antioxidant (A) is one or more diphosphates having a number average molecular weight of greater than 600 and having a neat toxicological profile, including pentaerythritol diphosphates of formula (III) and diphosphonites of formula (IV):
in these formulae, R2And R3Examples of suitable substituents are independent substituents selected from C8-22 alkanes, C8-22 alkenes, phenyl, C7-40 alkaryl and C7-40 aralkyl.
Examples of such bisphosphates include, but are not limited to:
(a) bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, CAS #: 154862-43-8, molecular weight 852, molecular structure
(b) Bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, CAS #: 80693-00-1, molecular weight 632, molecular structure of
(c) Bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, CAS #: 26741-53-7, molecular weight 604, molecular structure
(d) Tetrakis (2, 4-di-tert-butylphenol) -4, 4' -biphenyldiphosphite, CAS #: 119345-01-6, molecular weight 1035, and molecular structure
The diphosphates used in the thermoplastic composition are preferably bis (2, 4-cumylphenyl) pentaerythritol diphosphite and tetrakis (2, 4-di-tert-butylphenol) -4, 4' -biphenyldiphosphite having a number average molecular weight of more than 800, and more preferably bis (2, 4-dicumylphenyl) pentaerythritol diphosphite having the molecular structure of pentaerythritol diphosphite.
The antioxidant (B) is one or more hindered phenols, and the hindered phenols refer to organic compounds containing at least one phenol group. The hindered phenol suitably has a molecular weight of at least about 300, preferably at least about 500, more preferably at least about 600. Most preferred are hindered phenols containing a molecular structure containing an amide group (-NHCO-) and having low volatility at the processing and product service temperatures of the thermoplastic composition, may be further characterized by a 10% TGA thermal weight loss temperature of at least 260 ℃, preferably at least 300 ℃, and most preferably at least 350 ℃.
The hindered phenols have a clean toxicological profile including, but not limited to:
(a) pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], CAS #: 6683-19-8, molecular weight 1177, molecular structure
(b) Octadecyl (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, CAS #: 2082-79-3, molecular weight 530, molecular structure
(c) N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, CAS #: 23128-74-7, molecular weight 637, structural formula
(d)1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, CAS #: 1709-70-2, molecular weight 775, structural formula
(e) Triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], CAS #: 36443-68-2, molecular weight 587, structural formula
(f)1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, CAS #: 27676-62-6, molecular weight 784, structural formula
The hindered phenol used in the thermoplastic composition is most preferably N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine.
The mass ratio of the antioxidant (B) to the antioxidant (A) is preferably 1-3: 6, or even more preferably 1-2: 6.
the thermoplastic composition is a melt-prepared blend, and is blended and processed by using a single-screw or double-screw extruder. The processing steps are that the polyamide substrate slices and the functional auxiliary agents are added into a main feeding port (a first section feeding port) of an extruder all at once or are gradually added in a batch mode, and the glass fibers are added into a feeding port on the side of the middle section of the extruder. All the combinations are fully mixed by an extruder screw, and then are subjected to extrusion bracing, granulation and drying to obtain the composition.
In another aspect, the present invention relates to a molded article obtained by shaping the thermoplastic composition of the present invention. Examples of articles are water heating industry products and fittings such as water pipes, valves, fittings, faucets and water meters, automotive parts or engine parts. The product is made by injection molding.
The invention has the beneficial effects that:
1. polyamide (PA) is a polymer whose main chain contains a polar amide group (- [ NHCO ] -). The existing research and test results show that the aliphatic polyamide degradation products mainly comprise methyl end groups, formamide aldehyde and terminal olefin, the carboxyl content of the degraded end is increased, and the amino end group content is reduced. The above phenomena indicate that the degradation of aliphatic polyamides is mainly due to the C-C bond occurring at the terminal carboxyl group. In an aqueous environment, hydrolysis is the main mode causing degradation of polyamide, and particularly, the degradation speed is obviously accelerated under high temperature and acidic conditions. In order to delay the hydrolysis of polyamide materials, the existing technical method is mainly to add various functional aids (such as a heat stabilizer, a hydrolysis-resistant aid, a hydrophobic and oleophobic aid and the like). The disadvantage of this solution is that most functional aids are easily migratable and do not meet food contact safety standards. In general, an auxiliary agent with a higher proportion is required to be added to meet the long-term hydrolysis resistance function of the material, so that the material cannot be adequately applied to the field of sanitation and safety. To ensure that the material is sufficiently "clean", the addition of auxiliaries must be reduced, but this solution often results in a material that does not have long-term degradation resistance. According to the invention, the polyamide 66 with higher content of terminal amino groups is selected as a base material, and a large number of experimental comparisons show that the long-term hydrolysis resistance of the composition can be remarkably improved by improving the terminal amino groups of the polyamide 66, and the mechanical property retentivity of the composition after water absorption can be improved by adding the long carbon chain aliphatic polyamide.
2. The thermoplastic composition of the invention can have high stability against hydrolysis by only adding a small proportion of functional additives. In various embodiments of the present invention, the thermoplastic composition has a tensile strength retention of at least 50% after soaking in hot chlorinated water (Cl content 5ppm) at 90 ℃/1000 hours, based on comparison to an oven-dried state control, and the selected additives are superior in migration resistance, water extraction resistance and hydrolysis resistance to conventional antioxidants due to their special structure and relative molecular mass. However, the migration of additives in thermoplastic compositions is still unavoidable, and a further advantage of thermoplastic compositions is that the selected auxiliaries have a safe toxicological profile, meet the domestic and foreign hygiene safety requirements and are very pure compositions.
Detailed Description
The invention is further illustrated by the following examples. It is to be understood that the following examples are for illustrative purposes only and are not intended to limit the present invention.
The following materials were used in the examples and comparative examples:
PA66-1 refers to
U4800NC01 from Invitroda (INVISTA) with terminal amino groups of about 50mmol/kg and terminal carboxyl groups of about 80 mmol/kg.
PA66-2 refers to
21Z-NT01a2 from orlandd (ASCEND) having terminal amino groups of about 75mmol/kg and terminal carboxyl groups of about 55 mmol/kg.
PA66-3 refers to EP158NH from Huafeng group, which has about 85mmol/kg of terminal amino groups and about 45mmol/kg of terminal carboxyl groups.
PA610 refers to
XS1261, obtained from swiss chemical (EMS).
PA612 refers to
151L from DuPont (DUPONT).
PA1010 refers to
BS1358, obtained from the winning industry group (evonik industries sag).
PA1012 refers to
11, available from john, su.
PA11 refers to
BMNO, obtained from Arkema (ARKEMA).
PA12 refers to
L20, available from Switzerland chemistry (EMS).
PA1212 refers to Tochenesen PA1212, which is available from Tochenesen.
The long carbon chain PA mixture refers to a mixture of PA610/PA612/PA1010/PA1012/PA11/PA12/PA1212 in the same proportion, and is mixed by the Jinlun company.
GF-1 refers to chopped glass fiber OCV983-10P from OwensCoringVetrotex (OwensCoringVetrotex) with a circular cross-section and a filament diameter of 10 μm (manufacturer's nominal value).
GF-2 is a chopped glass fiber CSG3PA-820 obtained from Nippon province, having a cross-sectional ratio of 4, a cross-sectional major axis of 28 μm and a cross-sectional minor axis of 7 μm (manufacturer's nominal value).
PE/MAH refers to ethylene-maleic anhydride copolymer
E60, from Van der Rous (Vertellus).
AO-1 is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite
S-9228, available from Doverchemical corporation, Doverchemical chemical corporation.
AO-2 means bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphoric acid
PEP-36 from Adideco (ADEKA).
AO-3 is bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite
626 from adivant (Addivant).
AO-4 is tetrakis (2, 4-di-tert-butylphenol) -4, 4' -biphenyldiphosphite
P-EPQ from Clariant.
AO-5 is tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester
1010 from BASF (BASF).
AO-6 means octadecyl (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate
1076 from BASF (BASF).
AO-7 refers to N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine
1098 from BASF.
AO-8 means 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene
1330 from BASF (BASF).
AO-9 is diethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate]
245 from BASF (BASF).
AO-10 means 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid]
3114 from BASF.
AO-11 refers to a mixture of cuprous halide/potassium halide/stearate
H317 from Bruggemann (Bruggemann).
Stabilizer mixture 1 is a mixture of AO-1/AO-2/AO-3/AO-4 in the same ratio, mixed by the company of Jinlun.
The stabilizer mixture 2 is a mixture of the same proportions of AO-5/AO-6/AO-7/AO-8/AO-9/AO-10, mixed by the company of Jinlun.
Preparation method
Weighing the components according to the composition shown in Table 1, adding polyamide resin and additives into a main feeding port of a double-screw extruder, adding glass fiber from a side feeding port of the extruder through a forced feeding machine, setting the processing temperature to be 260-70 ℃, setting the screw rotating speed to be 250-350rpm, vacuumizing the melt at the penultimate section of the neck mold, and controlling the vacuum degree to be 50-70 cm-Hg. Extruding the composition after shearing and mixing, drawing and pulling strips, cooling, removing metal, drying, homogenizing and packaging. When packaging, the moisture content of the material is ensured to be less than 0.2 wt%.
Specimen molding and conditioning
The molding and conditioning of the test specimens were carried out in accordance with the method specified in ISO16396-2, with a molding melt temperature of 290 ℃ and 300 ℃ and a mold temperature of 80 ℃. The DAM state requires that the test piece is sealed in an aluminum foil bag after being molded, and is stored in an environment with the temperature of 23 +/-2 ℃ for more than 16 hours, and the water content of the test piece is ensured to be less than 0.2 percent.
Mechanical Property test
Tensile properties were determined according to ISO527-2, test specimens 1A, 170mm X10 mm X4 mm, tensile modulus tensile rate 1mm/min, tensile strength and elongation at break 5 mm/min.
Hydrolysis resistance test
The sample is completely immersed in an aqueous solution of 5ppm chlorine (prepared by blending sodium hypochlorite solution with purified water), the container must be sealed, and the solution is heated to 90 + -2 deg.C, during which time the solution needs to be replaced every 24 hours. Sampling is carried out at a plurality of sampling time points, the test medium is cooled to normal temperature during sampling, then the sample is taken out, the mechanical property test of the sample is completed within 30 minutes, the surface of the sample is observed, and the solution needs to be replaced after each sampling.
Migration resistance test
The sample was completely immersed in water (50. + -.2). degree.C.and boiled in water for 24 hours, taken out and dried at (120. + -.2). degree.C.for 24 hours, and then stored in a constant temperature and humidity chamber and conditioned at (60. + -.2). degree.C./(90. + -.10)% rh for 200 hours. After the test, the surface of the test specimen was observed after being taken out.
Examples and comparative examples
Table 1 lists the compositions of examples 1 to 4 and comparative examples 1 to 4.
Examples 2, 3, 1 and 2 show the hydrolysis resistance of polyamides 66 with different content of amino and carboxyl end groups in hot chlorine water. These examples and comparative examples show that the content of terminal amino groups and terminal carboxyl groups of the polyamide substrate increases. PA66-1 is a general-purpose polyamide 66 having about 50mmol/kg of terminal amino groups and about 80mmol/kg of terminal carboxyl groups, and the composition based on the resin in comparative example 1 has cracks after soaking in hot chlorine water at 90 ℃ for 500h and cracks after 1000h and loses function completely. In comparative example 2, reference examples 2 and 3 added proper amount of functional assistant, but the tensile strength retention rate of 500h was only 35.1%, and the test piece cracked after 1000 h. In examples 2 and 3 using high-end amine type PA66-2 and PA66-3 as base materials, the tensile strength retention of the composition can still be maintained above 50% after 1000h, and the hydrolysis resistance of the composition is remarkably improved. In particular, example 3, PA66-3 substrate was selected having the highest amino end group content of about 85mmol/kg and the lowest carboxyl end group content of about 45mmol/kg, which is superior to example 2 in resistance to hot chlorine water.
Examples 1, 4 and 3 show the resistance of the compositions to hydrolysis in hot chlorinated water with varying glass fiber content and long carbon chain polyamides. These examples and comparative examples show that as the proportion of glass fibres increases, the mechanical properties retained in hot water are also better, this being mainly the fact that the glass fibres increase on the one hand the initial mechanical properties of the composition and on the other hand reduce the water absorption of the composition. The long carbon chain polyamide PA610 is used for the substrate of comparative example 3, and shows excellent hydrolysis resistance, however, the cost is high and the initial mechanical properties are low when the long carbon chain polyamide is added in an excessive amount.
Comparative example 4 and comparative example 1 show that the hydrolysis resistance of the halide salt stabilizer is improved, and the hydrolysis resistance is remarkably improved by adding the halide salt stabilizer, but the halide salt stabilizer is easy to precipitate, so that the halide salt stabilizer is not suitable for the field of sanitary contact products.
TABLE 1
Remarking:
a. -representing slight cracking of the test piece;
b. x represents that the test piece has obvious cracking or corrosion;
c.O represents no precipitation of the material on the surface of the test piece;
d. delta represents that a substance was observed to be precipitated on the surface of the test piece.
Claims (6)
1. The application of the pure hydrolysis-resistant polyamide composition in water heating industry products and accessories of water pipes, valves, joints, faucets and water meters is characterized in that the pure hydrolysis-resistant polyamide composition comprises the following components in percentage by mass:
(a)40 to 84.80wt% of polyamide A,
(b) 15-60.00wt% of glass fiber,
(c) 0.10 to 0.50 weight percent of ethylene-maleic anhydride copolymer,
(d) 0.10 to 0.30 weight percent of antioxidant A,
(e) 0.10 to 28.00wt% of polyamide B,
(f) 0.01 to 0.30 weight percent of antioxidant B,
wherein the sum of the mass percentages of the component (a) to the component (f) is 100 wt%;
the ethylene-maleic anhydride copolymer is prepared by mixing ethylene and maleic anhydride in a molar ratio of 1: 1, the number average molecular weight is 50000-70000;
the mass ratio of the polyamide B to the polyamide A is 1-2: 4, the polyamide A is polyhexamethylene diamine adipate with more than 80mmol/kg of terminal amino groups or less than 50mmol/kg of terminal carboxyl groups, and the polyamide B is a mixture of one or more aliphatic long carbon chain polyamides;
the mass ratio of the antioxidant B to the antioxidant A is 1-3: 6;
the antioxidant A is one or moreA mixture of several bisphosphates having a number average molecular weight greater than 600 and comprising the structures of pentaerythritol diphosphate and diphosphonite of formula (iii):
(Ⅲ)、
(IV) in the formula, R2And R3Is an independent substituent selected from C8-22Alkane, C8-22Alkene, phenyl, C7-40Alkylaryl and C7-40Aralkyl group;
the antioxidant B is a mixture of one or more hindered phenols, has a number average molecular weight of more than 300, contains an amide group-NHCO-containing molecular structure, and is characterized by 10% TGA thermal weight loss temperature of at least 260 ℃.
2. Use according to claim 1, characterized in that the polyamide B is selected from the group consisting of: polyhexamethylene sebacamide, polyhexamethylene dodecanoamide, decamethylenesebacamide, decamethylenedodecanoamide, polyundecanoamide, polydodecanoamide and polydodecanedicarbamide.
3. The use according to claim 1, wherein the antioxidant A is selected from the group consisting of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite and tetrakis (2, 4-di-tert-butylphenol) -4, 4' -biphenylyl diphosphite.
4. The use according to claim 1, wherein the antioxidant B is selected from the group consisting of pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], octadecyl (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, N, one or a combination of two or more of N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, diethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ] and 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid.
5. Use according to claim 1, wherein the glass fibers are glass fibers with a circular cross-section or glass fibers with a profiled cross-section:
the monofilament diameter of the glass fiber with the circular section is 5-20 μm;
the cross section of the glass fiber with the special-shaped cross section is elliptical or polygonal, the short diameter of the cross section is 3-13 mu m, and the long diameter of the cross section is 10-50 mu m.
6. Use according to claim 5, wherein the round section glass fibers have a filament diameter of 7-17 μm.
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