WO2022110678A1 - Polymer composition for optical fiber connector structural member and preparation method therefor - Google Patents

Abstract

Disclosed in the present invention are a polymer composition for an optical fiber connector structural member and a preparation method therefor. The polymer composition comprises the following components: polyarylethersulfone, polyetheretherketone, and a reinforcing filler, wherein the polyarylethersulfone is polyethersulfone or a mixture of polyethersulfone and polyphenylene sulfone; the polyethersulfone is composed of repeating units of a group as shown in formula (I), the polyphenylene sulfone is composed of repeating units of a group as shown in formula (II), and the polyetheretherketone is composed of repeating units of a group as shown in formula (III). According to the present invention, the polyarylethersulfone, the polyetheretherketone and the reinforcing filler are matched with one another, to prepare the polymer composition having high strength, high toughness, excellent bending fatigue resistance and excellent environmental stress cracking resistance.

Description

A kind of polymer composition for optical fiber connector structure and preparation method thereof technical field

The present invention relates to the field of macromolecular polymers, and more particularly, to a polymer composition for optical fiber connector structural parts and a preparation method thereof.

Background technique

Optical fiber communication has become one of the important pillars of modern communication and plays a pivotal role in modern telecommunication networks. Optical fiber connector is a detachable connection device between optical fiber and optical fiber. It precisely butts the two end faces of the optical fiber, so that the light energy output by the transmitting fiber can be coupled to the receiving fiber to the maximum extent, and the It intervenes in the optical link to minimize the impact on the system. Classified by type, fiber optic connectors include FC type, SC type, ST type, E2000 type, LC type and MU type.

Fiber optic connector housings are typically fabricated from polymeric materials. Generally speaking, optical fiber connectors need to have resistance to cyclical high temperature, humidity and heat aging and high mechanical stability, which requires polymer materials to have good temperature resistance, aging resistance and excellent mechanical properties. Chinese patent application CN102282204A discloses a high-performance connector with higher heat resistance. The high-performance connector, comprising a polymer composition consisting of polyetherketoneketone and inorganic nanotubes, can be used as a fiber optic connector in high temperature operating conditions, but its resistance to environmental stress and fatigue has not been focused.

With the gradual development of 5G infrastructure, higher requirements have been placed on the performance of optical connector materials. The optical fiber connector must have better resistance to environmental stress cracking in the use environment, and can withstand the operating conditions of multiple bending, and has good fatigue resistance. Polyetheretherketone has excellent fatigue and chemical resistance, but polyetheretherketone is a very expensive material known to those skilled in the art. Chinese patent application CN110229493A discloses a polymer composition, the specification of which states that the polymer composition comprises at least one polyether ether ketone, at most 45 wt.% of an aromatic sulfone polymer, at least one reinforcing filler, the polymer The composition has good stiffness, toughness, elongation and excellent chemical resistance. However, the resin matrix of the polymer composition is polyether ether ketone, and the cost is too high, so it is difficult to popularize and apply to large-scale industrial production.

Therefore, there is a need to develop a polymer composition with excellent fatigue resistance, environmental stress crack resistance, and lower cost.

SUMMARY OF THE INVENTION

The present invention provides a polymer composition for optical fiber connector structural parts in order to overcome the defects of the prior art that the polymers for optical fiber connectors have bending fatigue resistance, environmental stress cracking resistance and low cost. The polymer composition has excellent resistance to bending fatigue and environmental stress cracking, and is relatively low cost.

Another object of the present invention is to provide a method for preparing the above-mentioned polymer composition.

Another object of the present invention is to provide the application of the above-mentioned polymer composition in the preparation of optical fiber connector structural parts.

In order to solve the above-mentioned technical problems, the technical scheme adopted in the present invention is:

A polymer composition for an optical fiber connector structure, comprising the following components by weight:

100 parts of polyaryl ether sulfone (PAES),

Polyetheretherketone (PEEK) 0～60 parts,

1 to 25 parts of reinforcing filler;

Wherein PAES is polyethersulfone (PES), or a mixture of polyethersulfone and polyphenylenesulfone (PPSU);

The PES consists of repeating units of the group of formula (I):

The PPSU consists of repeating units of the group of formula (II):

Said PEEK consists of repeating units of the group of formula (III):

Preferably, the PES has a melt flow rate (MFR) ≥ 40 g/10min at 380°C under a load of 2.16 kg according to ISO 1133-2011.

Optionally, the PES is Visulfon C001, Visulfon C002 and Visulfon C003 of Kingfa Technology Co., Ltd.

Preferably, the PPSU polymer has an MFR ≥ 10 g/10 min at 365°C under a load of 5 kg according to ISO 1133-2011.

Optionally, the PPSU is Visulfon B001, Visulfon B002 and Visulfon B003 of Kingfa Technology Co., Ltd.

The PEEK is a crystalline aromatic ether ketone polymer. Preferably, the PEEK polymer has an MFR > 10 g/10min at 380°C under a load of 2.16 kg according to ISO 1133-2011.

Optionally, the PEEK is Vispeek 9001G, Vispeek 9002G and Vispeek 9003G of Kingfa Technology Co., Ltd.

When the PAES is a mixture of PES and PPSU, preferably, the PPSU is 0-50 parts by weight.

The rigidity of PEEK is better than that of PES. Adding PEEK to PES can significantly improve the rigidity of the material. At the same time, due to the interaction between the molecular chains of PES and PEEK, the entanglement of the molecular chains will reduce the crystallinity of PEEK and make the material tougher. There will also be a significant lifting effect, achieving material enhancement and toughening at the same time. By adding PPSU, the compatibility of the system is further improved, so that the comprehensive properties of the polymer composition are further improved.

In the case that the polymer composition does not contain PEEK, the inventors have found through extensive research that a polymer composition with good bending resistance and environmental stress crack resistance can be obtained by selecting a suitable reinforcing filler. In the case of further adding PEEK, because the PEEK material itself has excellent resistance to bending and environmental stress cracking, the polymer composition has excellent resistance to bending fatigue, according to the ASTM D7791-2017 method at a frequency of 5Hz Bending fatigue performance test, failure times ≥ 6×10 ³ ; and excellent environmental stress cracking resistance, using 10% concentration of Igepal CO630 reagent to conduct environmental stress cracking resistance test according to GB T1842-2008 method, the damage rate is 50 % of the time F50 ≥ _196h .

Preferably, the PEEK is preferably 5-50 parts by weight.

More preferably, the PEEK is preferably 11-42 parts by weight.

Most preferably, the PEEK is preferably 17-33 parts by weight.

The amount of PEEK added in the polymer composition affects the rigidity and toughness of the polymer composition. When there is too much PEEK, it is difficult to fully interact between PES and PEEK, which will lead to a significant decrease in the elongation at break and the toughness of the material. The inventors have further researched and found that with a suitable amount of PEEK added, the polymer composition can have high strength and toughness, and at the same time have excellent bending fatigue resistance and environmental stress cracking resistance.

When the added amount of PEEK is 0, the polymer composition can also have good bending fatigue resistance and environmental stress cracking resistance.

Because different types of connectors have different requirements for material properties, for example, connectors for indoor applications have lower requirements for environmental stress cracking resistance, while connectors for outdoor use have higher requirements for environmental stress cracking resistance. Therefore, although the overall performance of the polymer composition without PEEK in the technical solution of the application is slightly lower than that of the polymer composition containing PEEK, it still has good resistance to environmental stress cracking and can meet the connection requirements of specific application scenarios. device material requirements.

Preferably, the reinforcing filler is preferably a mineral filler with a flaky structure.

Preferably, the average particle size of the mineral filler is 0.1-100 μm.

PAES is an amorphous material and is isotropic. During the bending process, the strength and modulus perpendicular to the bending force direction are small. By adding sheet-like reinforcing fillers, on the one hand, the sheet-like fillers are oriented along the flow direction to improve the anisotropy of the material, so that the strength and modulus perpendicular to the flow direction are significantly improved, and the ability of the material to resist deformation is improved; on the other hand, in the During the bending process, the interface formed by the reinforcing filler and the polymer matrix can prevent the expansion of crazing caused by deformation and prevent the material from prematurely breaking. For the improvement of resistance to environmental stress cracking, the sheet-like reinforcing filler is oriented along the skin layer of the material during the injection molding process, which can effectively prevent the penetration of the solvent, prolong the time for the solvent to enter the core layer of the material, and effectively improve the failure time of the material. ; In addition, the interfacial layer between the reinforcing filler and the polymer can absorb the internal force generated during the molding process of the material, thereby improving the resistance to environmental stress cracking.

Preferably, the mineral filler is preferably one or more of kaolin, mica powder, talc, montmorillonite, bentonite, and platelet-shaped potassium titanate whiskers.

More preferably, the mineral filler is preferably montmorillonite.

The polymer composition may also include 0-5 parts by weight of auxiliary agents.

Optionally, the auxiliary agent is one or more of light stabilizers, antioxidants, pigments, and lubricants.

The light stabilizer is a light shielding agent, an ultraviolet absorber, a quencher, a free radical scavenger and a hydroperoxide decomposer;

The antioxidants are hindered phenol antioxidants, hindered amine antioxidants, phosphite antioxidants, thioester antioxidants, thiol antioxidants and metal deactivators;

The pigments are inorganic pigments and organic pigments, wherein inorganic pigments include metal oxides, sulfides, sulfates, chromates, molybdates and other salts, carbon black; organic pigments include azo pigments, phthalocyanine pigments, miscellaneous pigments. Ring pigments, lake pigments, dyes, fluorescent whitening agents, fluorescent pigments;

The lubricants are fatty acid amides, hydrocarbons, fatty acids, esters, alcohols, metal soaps and complex lubricants.

The present invention also protects the preparation process of the above-mentioned polymer composition.

When no auxiliary agent is added to the polymer composition, the preparation process includes the following steps:

The polyaryl ether sulfone, polyether ether ketone and reinforcing filler are mixed and then added to an extruder, and subjected to melt mixing, extrusion and granulation to obtain the polymer composition.

When an auxiliary agent is added to the polymer composition, the preparation process includes the following steps:

The polyaryl ether sulfone, the polyether ether ketone, the reinforcing filler and the auxiliary agent are mixed and then added to the extruder, and the polymer composition is obtained by melt mixing, extrusion and granulation.

Preferably, the extruder is one of a kneader, an internal mixer, a single-screw extruder or a twin-screw extruder.

The present invention also protects the application of the above-mentioned polymer composition in the preparation of structural parts of optical fiber connectors.

The structure of the fiber optic connector includes a housing or an invisible internal structure of the fiber optic connector. The optical fiber connector is an FC type, SC type, ST type or LC type optical fiber connector.

Compared with the prior art, the beneficial effects of the present invention are:

The present invention prepares a polymer composition with high strength and high toughness, excellent bending fatigue resistance and environmental stress cracking resistance by cooperating PAES, PEEK and reinforcing filler. The optical fiber connector structure prepared from the polymer composition can adapt to a more severe operating environment without being easily cracked or damaged, has good fatigue resistance, and can withstand more repeated bending operations.

Detailed ways

The present invention will be further described below in conjunction with specific embodiments.

The raw materials in the embodiment and the comparative example can be obtained by commercially available, as follows:

Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.

Examples 1 to 24

The content of each component in the polymer compositions of Examples 1 to 24 is shown in Table 1.

The preparation method is as follows: according to Table 1, add each component into a high-speed mixer to mix evenly, put it into a twin-screw extruder after drying at 120°C for 4 hours, and extrude by melt granulation, extrusion temperature 380°C, rotation speed: 400rpm , to obtain a polymer composition.

Table 1 Component content (parts by weight) of the polymer compositions of Examples 1-24

	1	2	3	4	5	6	7	8	9	10	11	12	13	14
PES-A	100	100	100	100	100	100	100	100	100	100	-	40	50	75
PES-B	-	-	-	-	-	-	-	-	-	-	50	-	-
PPSU	-	-	-	-	-	-	-	-	-	-	50	60	50	25
PEEK	-	-	5	11	17	33	42	50	60	60	33	33	33	33
Montmorillonite	1	10	10	10	10	10	10	10	1	25	10	10	10	10

Table 1 Continued Examples 1-20 Component content (parts by weight) of polymer compositions

Comparative Examples 1 to 8

The content of each component in the polymer compositions of Comparative Examples 1-8 is shown in Table 2.

The preparation method is as follows: according to Table 2, add each component to a high-speed mixer to mix evenly, put it into a twin-screw extruder after drying at 120°C for 4 hours, and extrude by melt granulation, extrusion temperature 380°C, rotation speed: 400rpm , to obtain a polymer composition.

Table 2 Component content (parts by weight) of the polymer compositions of Comparative Examples 1 to 8

	1	2	3	4	5	6	7	8
PES	100	-	-	-	100	100	75	100
PPSU	-	100	-	-	-	-	25	-
PEEK	-	-	60	50	80	-	-	11
Montmorillonite	-	-	-	10	10	30	30	30

Performance Testing

The properties of the polymer compositions prepared in the above examples and comparative examples were tested.

The polymer compositions prepared in the above examples and comparative examples were injection-molded into test specimens according to _ISO527 , and their tensile strength, elongation at break, failure times of bending fatigue performance, and environmental stress cracking resistance F50 were tested.

The test method is as follows:

Tensile strength: ISO 527-2-2012;

Elongation at break: ISO 527-2-2012;

Bending fatigue performance failure times: ASTM D7791-2017, frequency 5Hz;

Environmental stress cracking resistance F50: GB _T1842-2008 , Igepal CO630 is used as the reagent, the concentration is 10%, and the time to calculate the breakage rate is 50%.

The test results of Examples 1 to 24 are shown in Table 3.

Table 3 Performance test results of Examples 1 to 24

According to the test results in Table 3, the polymer compositions prepared in Examples 1 to 20 of the present application all have good rigidity-toughness balance, excellent bending fatigue resistance and environmental stress cracking resistance. The test specimens made of the polymer composition have bending fatigue performance failure times ≥4.3×10 ³ , and environmental stress cracking resistance F ₅₀ ≥102.6h.

According to Examples 2 to 8, the content of PEEK has a certain influence on the rigidity and toughness, bending fatigue resistance and environmental stress cracking resistance of the polymer composition. When the amount of PEEK is 11-42 parts by weight, the polymer composition has good rigidity-toughness balance, bending fatigue resistance and environmental stress cracking resistance; when the amount of PEEK is 17-33 parts by weight, the comprehensive The performance is better, in which the tensile strength is greater than or equal to 110MPa, the elongation at break is greater than or equal to 80%, the number of failures in bending fatigue performance is greater than or equal to 10.9×10 ³ , and the environmental stress cracking resistance F ₅₀ is greater than or equal to 325h.

According to Examples 12 to 14, the addition of PPSU further improves the overall properties of the polymer composition, and preferably PPSU accounts for at most 50 wt. % of the PAES.

According to Examples 14-23, in the case of the same content of PES, PPSU and PEEK, when the filler is a compound of montmorillonite, mica powder, talc, kaolin and flaky potassium titanate whiskers, the polymer composition It has better resistance to bending fatigue and environmental stress cracking; when the filler is montmorillonite, the polymer composition has better resistance to bending fatigue and environmental stress cracking.

The test results of Comparative Examples 1 to 8 are shown in Table 4.

Table 4 Performance test results of comparative examples 1 to 8

According to Comparative Examples 1 to 3, without adding fillers, the bending fatigue resistance and environmental stress cracking resistance of pure PES and pure PPSU are poor, and it is difficult to meet the actual needs; Environmental stress cracking resistance meets the requirements, but the elongation at break is only 45%, and the cost of PEEK is high. The polymer composition of Comparative Example 4 does not contain PES, and the polymer composition of Comparative Example 5 contains too much PEEK. The two polymer compositions have low elongation at break and still have the disadvantage of high cost. According to Comparative Examples 6 to 8, when the filler content is too large, the toughness, bending fatigue resistance and environmental stress cracking resistance of the polymer composition are all poor.

Obviously, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, rather than limiting the embodiments of the present invention. For those of ordinary skill in the art, changes or modifications in other different forms can also be made on the basis of the above description. There is no need and cannot be exhaustive of all implementations here. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention shall be included within the protection scope of the claims of the present invention.

Claims (10)

1. A polymer composition for optical fiber connector structural parts, characterized by comprising the following components by weight: 100 parts of polyaryl ether sulfone, 0 to 60 parts of polyether ether ketone, and 1 to 25 parts of reinforcing filler;

   Wherein the polyaryl ether sulfone is polyether sulfone, or a mixture of polyether sulfone and polyphenylene sulfone;

   The polyethersulfone is composed of repeating units of the group of formula (I):

   

   The polyphenylene sulfone is composed of repeating units of the group of formula (II):

   

   The polyetheretherketone is composed of repeating units of the group of formula (III):

   
2. The polymer composition according to claim 1, wherein the polyphenylene sulfone is 0-50 parts by weight.
3. The polymer composition according to claim 1, wherein the polyether ether ketone is 5-50 parts by weight.
4. The polymer composition according to claim 1, characterized in that the polyethersulfone has a melt flow rate ≥ 40 g/10 min at 380° C. and a load of 2.16 kg according to ISO 1133-2011.
5. The polymer composition according to claim 1, wherein the polyphenylene sulfone has an MFR≥10g/10min at 365°C under a load of 5kg according to ISO 1133-2011.
6. The polymer composition according to claim 1, wherein the reinforcing filler is a mineral filler with a lamellar structure.
7. The polymer composition according to claim 6, wherein the mineral filler is one or more of kaolin, mica powder, talc, montmorillonite, bentonite, and flaky potassium titanate whiskers.
8. The preparation method of the polymer composition according to any one of claims 1 to 7, characterized in that, comprising the steps of:

   The polyaryl ether sulfone, polyether ether ketone and reinforcing filler are mixed and then added to an extruder, and subjected to melt mixing, extrusion and granulation to obtain the polymer composition.
9. Application of the polymer composition according to any one of claims 1 to 7 in the preparation of a structural member of an optical fiber connector.
10. The application according to claim 9, wherein the optical fiber connector is an FC-type, SC-type, ST-type or LC-type optical fiber connector, and the structural member is a housing and/or an invisible optical fiber connector. Internal structural parts.