CN114940858B

CN114940858B - Special outer coating layer for guidance optical cable

Info

Publication number: CN114940858B
Application number: CN202210676279.XA
Authority: CN
Inventors: 黄星; 余晓梦; 崔丽云; 万欢; 桂振东; 高旭
Original assignee: Wuhan Changyingxin Technology Co ltd
Current assignee: Wuhan Changyingxin Technology Co ltd
Priority date: 2022-06-15
Filing date: 2022-06-15
Publication date: 2023-03-14
Anticipated expiration: 2042-06-15
Also published as: CN114940858A

Abstract

The invention provides a special outer coating layer for a guidance optical cable, which is suitable for a production line of UV-LED, mercury lamp and microwave electrodeless lamp ultraviolet curing, and comprises the following components in percentage by weight: 40-75% of self-initiation multifunctional epoxy acrylic resin, 15-25% of acrylamide monomer, 5-15% of N-vinyl monomer, 5-10% of adhesion promoting resin and 0-10% of UV color paste, wherein the sum of the components is 100%; the special outer coating layer for the guide optical cable is specially developed for the guide optical cable with a specific structure, has high glass transition temperature (higher than 100 ℃), high strength and high wear resistance, can meet the actual application requirement of high-speed paying-off, and has no adverse effect on optical fiber signal transmission.

Description

Special outer coating layer for guidance optical cable

Technical Field

The invention belongs to the field of optical fibers and optical cables, and particularly relates to a special outer coating layer for a guidance optical cable.

Background

The guided missile guided by the method does not worry that the information in the emission is intercepted by enemies, is very important for the information safety of a battlefield, and can realize the accurate strike of a target.

The guiding optical cable is wound on a pay-off reel according to a certain rule when in application, and the high-speed pay-off friction is needed from the pay-off reel when in high-speed pay-off, so that the special outer coating layer for the guiding optical cable needs to have high strength and high wear resistance, has higher glass transition temperature, has no adverse effect on the signal transmission of the optical fiber, and needs to have very good adhesive force on the high-strength fiber and a matched special inner coating layer.

Disclosure of Invention

The invention aims to solve the technical problem of providing a special outer coating layer for a guidance optical cable aiming at the application requirements, and the special outer coating layer has proper viscosity and can be suitable for the special coating process of the guidance optical cable.

The technical scheme adopted by the invention is as follows:

a special outer coating layer for a guidance optical cable comprises the following components in percentage by weight: 40-75% of self-initiation multifunctional epoxy acrylic resin, 15-25% of acrylamide monomer, 5-15% of N-vinyl monomer, 5-10% of adhesion promoting resin and 0-10% of UV color paste, wherein the sum of the components is 100%.

According to the scheme, the preparation method of the self-initiated multifunctional epoxy acrylic resin comprises the following steps:

1) Adding a mol of AG-80 epoxy resin, b mol of 2-carboxyethyl acrylate and c mol of itaconic acid monoester into a reactor with mechanical stirring, uniformly stirring, adding a certain mass of N-vinyl monomer, then adding a catalyst accounting for 0.1-0.5% of the total mass of the raw materials in the step and a polymerization inhibitor accounting for 0.01-0.5% of the total mass of all the raw materials in the step, heating to 90-120 ℃, and carrying out heat preservation reaction for 1-8 hours to obtain an epoxy acrylate intermediate; wherein, a (b + c) = 1.3.9-1, b: c = 1:1-3; in the step, the total mass of all the raw materials refers to the sum of the masses of AG-80 epoxy resin, 2-carboxyethyl acrylate, itaconic acid monoester and N-vinyl monomer;

2) Mixing a photoinitiator 2959 with the total mole number of c mol and a photoinitiator R-GEN 988 according to a certain proportion, then adding c mol of diisocyanate, uniformly stirring, adding dibutyltin dilaurate accounting for 0.01-0.2% of the total mass of the raw materials in the step, and reacting for 1 hour at the temperature of 60-80 ℃ to obtain a photosensitive intermediate; in the step, the total mass of the raw materials refers to the sum of the mass of the photoinitiator 2959, the mass of the photoinitiator R-GEN 988 and the mass of the diisocyanate;

3) Uniformly mixing the epoxy acrylate intermediate obtained in the step 1) with the photosensitive intermediate obtained in the step 2) according to the mass ratio of 2.5-2:1, and reacting for 2 hours at 60-80 ℃ to obtain the self-initiated multifunctional epoxy acrylic resin.

Further, in the preparation method of the self-initiated multifunctional epoxy acrylic resin, the itaconic acid monoester includes but is not limited to one or more of itaconic acid monoalkyl ester, itaconic acid monocycle alkyl ester and the like in any proportion; wherein, the itaconic acid monoalkyl ester is selected from one or more of itaconic acid monomethyl ester, itaconic acid monoethyl ester, itaconic acid monopropyl ester, itaconic acid monobutyl ester and the like; the itaconic acid monocyclic alkyl ester is selected from one or more of itaconic acid monocyclic pentyl ester, itaconic acid monocyclic hexyl ester, itaconic acid monocyclic heptyl ester and the like.

Further, in the preparation method of the self-initiated multifunctional epoxy acrylic resin, the structural formula of the photoinitiator 2959 is shown as a formula 1, and the structural formula of the photoinitiator R-GEN 988 is shown as a formula 2.

Furthermore, in the preparation method of the self-initiation multifunctional epoxy acrylic resin, the catalyst is 4-dimethylamino pyridine and the like, and the polymerization inhibitor is p-hydroxyanisole and the like; the N-vinyl monomer includes but is not limited to one or more of N-vinyl pyrrolidone, N-vinyl o-phenyl imine, 3-acetyl-N-vinyl pyrrolidone, N-vinyl carbazole, N-vinyl caprolactam and the like in any proportion.

Furthermore, in the preparation method of the self-initiated multifunctional epoxy acrylic resin, the molar ratio of the photoinitiator 2959 to the photoinitiator R-GEN 988 is 1:1-3:1.

Further, in the preparation method of the self-initiated multifunctional epoxy acrylic resin, the diisocyanate includes, but is not limited to, 2,4 toluene diisocyanate, isophorone diisocyanate, and the like.

According to the scheme, the adhesion promoting resin has special double-ring and polyurea structures, is high in polarity, has very good adhesion to high-strength fibers and matched special internal coating layers, and has the structure shown as the formula 3:

according to the scheme, the preparation method of the adhesion promoting resin comprises the following steps:

1) Slowly adding d mol of norbornene-2-methylamine into a reactor containing e mol of 2,4-toluene diisocyanate, stirring while adding, and reacting for 1-3 hours at the temperature of 20-30 ℃;

2) F mol of N-hydroxyethyl acrylamide is continuously added into the reactor in the step 1), then a catalyst dibutyltin dilaurate accounting for 0.01-0.1% of the total mass of all the raw materials and a polymerization inhibitor p-hydroxyanisole accounting for 0.01-0.1% of the total mass of all the raw materials are added, and the reaction is maintained at the temperature of 60-80 ℃ for 2-6 hours, so that the adhesion promoting resin is obtained. Wherein d: e =1, e f = 1.

According to the scheme, the acrylamide monomer comprises one or more of N-p-hydroxyphenyl acrylamide, N '-vinyl bisacrylamide, N-benzyl acrylamide, N-dimethyl aminopropyl acrylamide, N-diethyl acrylamide, N- [ tri (3-acrylamide propyl methyl ether) methyl ] acrylamide, N' - (butane-1,4-diyl) bisacrylamide, N-phenyl acrylamide, hexamethylene bisacrylamide and the like according to any proportion.

According to the scheme, the N-vinyl monomer comprises one or more of N-vinyl pyrrolidone, N-vinyl o-phenyl imine, 3-acetyl-N-vinyl pyrrolidone, N-vinyl carbazole, N-vinyl caprolactam and the like which are mixed according to any proportion.

According to the scheme, the UV color paste is a special color paste which can be used for ultraviolet curing optical fiber coloring ink, namely, the UV color paste is prepared by dispersing pigment by using a UV monomer, and adding a small amount of dispersing agent and defoaming agent, wherein the pigment concentration is 8-70%, the defoaming agent is 0.001-2% and the dispersing agent is 1-30% by mass percent.

Suitable UV monomers include, but are not limited to, mixtures of any proportion of one or more of hexanediol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, and the like.

The invention also provides a preparation method of the special external coating layer for the guidance optical cable, which comprises the steps of weighing the raw material components according to the proportion, stirring the raw material components for 30 to 120 minutes at the rotating speed of 800 to 1500 revolutions per minute at the temperature of between 60 and 80 ℃, filtering the mixture by using a 500-mesh filter after the raw material components are completely and uniformly mixed, and defoaming the mixture in a 40-DEG C oven for 12 hours to obtain a finished product.

The invention also provides a guidance optical cable adopting the special external coating layer. The production process of the whole guidance optical cable comprises the following steps: covering the high-strength fiber on the surface of the high-strength optical fiber, then passing through a die filled with a special inner coating layer of the guidance optical cable, and then quickly curing the inner coating layer by using an ultraviolet curing lamp; and then, the optical cable coated with the special inner coating layer of the guide optical cable passes through a die filled with the special outer coating layer of the guide optical cable, and then the outer coating layer is rapidly cured by using an ultraviolet curing lamp to obtain the guide optical cable.

The special outer coating layer for the guide optical cable has the viscosity of 1000-10000mpa.s at 25 ℃, and the preferable viscosity is 2000-6000mpa.s. Compared with the prior art, the invention has the beneficial effects that:

first, the special outer coating layer for a guide optical cable of the present invention is developed specifically for a guide optical cable of a specific structure, and does not have an adverse effect on optical fiber signal transmission.

Secondly, the special outer coating layer for the guidance optical cable can adapt to the production line of UV-LED, mercury lamp and microwave electrodeless lamp, and has strong adaptability.

Thirdly, according to the practical application requirements of high-speed paying-off and use temperature of the guide optical cable, the outer coating is required to have high vitrification temperature (more than 100 ℃), high strength and high wear resistance, the invention designs an integral high-polarity system formula of self-initiated multifunctional epoxy acrylic resin matched with acrylamide monomers and N-vinyl monomers and assisted with adhesive force to promote the resin, realizes high cohesive force which cannot be realized by a traditional acrylate system (medium polarity), and realizes high strength, high vitrification temperature and high wear resistance.

Drawings

Fig. 1 shows a structure of a guide optical fiber according to the present invention. Wherein 1 is a high-intensity optical fiber for transmitting signals; 2, high-strength fibers (such as carbon fibers, aramid fibers, ultra-high-strength polyethylene fibers and the like) are used for bearing ultra-high tensile force in the guidance process; 3, a special inner coating layer of the guidance optical cable, which is mainly used for bonding the high-strength fiber and the high-strength optical fiber into a whole; 4 is the special outer coating layer for the guidance cable of the present invention, which mainly functions as the outermost layer to protect the entire cable.

Detailed Description

In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the present invention is not limited to the following examples.

Some of the specific raw materials used in the following examples are shown in table 1.

TABLE 1

In the following examples, the specific preparation methods of the self-initiated multifunctional epoxy acrylic resin and the adhesion promoting resin are as follows:

1. the preparation method of the self-initiated multifunctional epoxy acrylic resin comprises the following steps:

1) 446g (1 mol) of AG-80 epoxy resin, 360.325g (2.5 mol) of 2-carboxyethyl acrylate and 279.315g (1.5 mol) of monobutyl itaconate are added into a reactor with mechanical stirring, 217g of 3-acetyl-N-vinyl pyrrolidone is added after uniform stirring, then 3.1g of catalyst 4-dimethylamino pyridine and 1.7g of polymerization inhibitor p-hydroxyanisole are added, and the temperature is raised to 95-105 ℃ for heat preservation reaction for 3-4 hours to obtain an epoxy acrylate intermediate.

2) 112.125g (0.5 mol) of photoinitiator 2959 and 177.245 (0.5 mol) of photoinitiator R-GEN 988 are added into a reactor with mechanical stirring, 222.29g (1 mol) of isophorone diisocyanate is added and stirred uniformly, then 0.5g of dibutyltin dilaurate is added, and the reaction is maintained at 60-70 ℃ for 1 hour, so that a photosensitive intermediate is obtained.

3) Uniformly mixing 1000g of the epoxy acrylate intermediate obtained in the step 1) and 400g of the photosensitive intermediate obtained in the step 2), and reacting for 2 hours at the temperature of 70-75 ℃ to obtain the self-initiated multifunctional epoxy acrylic resin A-1.

2. Adhesion promoting resin synthesis

1) 132.2g (1 mol) of norbornene-2-methylamine are slowly charged into a reactor containing 174.16g (1 mol) of 2,4-tolylene diisocyanate, stirred while maintaining the temperature at 20-30 ℃ for 1.5-2 hours.

2) 120.88g (1.05 mol) of N-hydroxyethyl acrylamide is added into a reactor, 0.22g of dibutyltin dilaurate as a catalyst and 0.3g of p-hydroxyanisole as a polymerization inhibitor are added, and the mixture is kept at 70-80 ℃ for reaction for 2-3 hours to obtain the adhesion promoting resin F-1, wherein the structure is shown as a formula 3.

3. Preparation of white color paste

The contents of the components are as follows according to the weight percentage: 60 percent of titanium dioxide white, 3 percent of BYK-111 dispersant, 1 percent of BYK-093 defoamer and 36 percent of trimethylolpropane triacrylate, wherein the sum of the components meets 100 percent, and the specific preparation method is as follows: (1) Uniformly mixing trimethylolpropane triacrylate, BYK-111 and BYK-093 to obtain a mixed liquid component; then under the stirring state of 500r/min, adding titanium dioxide pigment into the mixed liquid component, after the pigment is added, raising the rotating speed to 1000r/min, and stirring for 1.0 hour to obtain UV rough color paste; (2) And grinding the UV rough color paste, measuring the fineness by using a laser particle size analyzer, and obtaining the UV white color paste for optical fiber coloring ink when all pigment particles are measured to be less than 1 micron.

4. Preparation of black color paste

The contents of the components are as follows according to the weight percentage: 20% of carbon black, 18% of BYK-163 dispersing agent, 1% of BYK-093 defoaming agent and 61% of trimethylolpropane triacrylate, wherein the sum of the components meets 100%, and the mixture is prepared according to a preparation method of white color paste and ground until all pigment particles are less than 1 micron.

5. Preparation of red color paste

The contents of the components are as follows according to the weight percentage: 20% quinacridone red, 8% byk-163 dispersing agent, 1% byk-093 antifoaming agent, 71% tripropylene glycol diacrylate, the sum of the components satisfying 100%, formulated according to the formulation method of white pastes and ground until all pigment particles are less than 1 micron.

Example 1

A special outer coating layer for a guidance optical cable comprises the following components in percentage by weight: the self-initiation multifunctional epoxy acrylic resin comprises, by weight, 56% of self-initiation multifunctional epoxy acrylic resin A, 5% of N-p-hydroxyphenyl acrylamide, 10% of N, N-diethyl acrylamide, 1% of N-benzyl acrylamide, 3% of N-vinyl o-phthalimide, 10% of 3-acetyl-N-vinyl pyrrolidone, 2% of N-vinyl carbazole, 1% of adhesion promoting resin F, 3% of white color paste, 2% of red color paste and 1% of black color paste, wherein the sum of the components is 100%;

the preparation method of the special outer coating layer for the guidance optical cable comprises the following steps: weighing the raw material components according to the proportion, stirring the raw material components for 60 minutes at the rotating speed of 1000r/min at about 70 ℃ by using a dispersion machine, filtering the mixture by using a 500-mesh filter after the raw material components are completely and uniformly mixed, and defoaming the mixture in a 40 ℃ oven for 12 hours to obtain a finished product with the viscosity of 25 ℃ of 3560mpa.s and the number of W-01.

Example 2

A special outer coating layer for a guidance optical cable comprises the following components in percentage by weight: the self-initiation multifunctional epoxy acrylic resin comprises 53.5% of self-initiation multifunctional epoxy acrylic resin A, 3% of N-p-hydroxyphenyl acrylamide, 15% of N, N-diethyl acrylamide, 2% of N-phenyl acrylamide, 3% of N-vinyl o-phthalimide, 5% of 3-acetyl-N-vinyl pyrrolidone, 2% of N-vinyl carbazole, 10% of adhesion promoting resin, 2% of white color paste, 4% of red color paste and 0.5% of black color paste, wherein the sum of the components is 100%;

the preparation method of the special outer coating layer for the guidance optical cable comprises the following steps: weighing the raw material components according to the proportion, stirring the raw material components for 60 minutes at the rotating speed of 1000r/min at about 70 ℃ by using a dispersion machine, filtering the mixture by using a 500-mesh filter after the raw material components are completely mixed uniformly, and defoaming the mixture in a 40 ℃ oven for 12 hours to obtain a finished product with the viscosity of 25 ℃ of 3120mpa.s and the number of W-02.

Example 3

A special outer coating layer for a guidance optical cable comprises the following components in percentage by weight: the self-initiation multifunctional epoxy acrylic resin comprises, by weight, 72% of self-initiation multifunctional epoxy acrylic resin A, 5% of N-p-hydroxyphenyl acrylamide, 2% of N, N' -vinyl bisacrylamide, 10% of N, N-dimethylacrylamide, 5% of 3-acetyl-N-vinyl pyrrolidone and 6% of adhesion promoting resin, wherein the sum of the components is 100%;

the preparation method of the special outer coating layer for the guide optical cable comprises the following steps: weighing the raw material components according to the proportion, stirring the raw material components for 60 minutes at the rotating speed of 1000r/min at about 70 ℃ by using a dispersion machine, filtering the mixture by using a 500-mesh filter after the raw material components are completely and uniformly mixed, and defoaming the mixture in a 40 ℃ oven for 12 hours to obtain a finished product with the viscosity of 25 ℃ 6230mpa.s and the number of W-03.

Performance test

The following examples 1-3 were tested for performance as shown in Table 2.

Table 2: comparison of typical values for examples 1-3

Note: preparation of a guided optical cable using the above outer coating layer samples of the guided optical cable were subjected to OTDR testing for attenuation before and after cabling at a wavelength band of 1310nm, wherein the diameter of the optical fiber was 250 μm, the diameter after coating the high-strength fiber and the inner coating layer was 320 μm, and the diameter after coating the outer coating layer was 350 μm.

As can be seen from the table 2, compared with the conventional optical fiber outer layer coating, the W-01 \/W-02 \/W-03 of the invention has the advantages of obviously higher glass transition temperature, better wear resistance and higher tensile strength, and can enable the guide optical cable to bear larger tensile force, and the prepared guide optical fiber sample has additional attenuation less than 0.02dB/km and has no adverse effect on signal transmission.

The above description of the present invention is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various modifications and changes without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.

Claims

1. A special outer coating layer for a guidance optical cable comprises the following components in percentage by weight: 40-75% of self-initiation multifunctional epoxy acrylic resin, 15-25% of acrylamide monomer, 5-15% of N-vinyl monomer, 5-10% of adhesion promoting resin and 0-10% of UV color paste, wherein the sum of the components is 100%;

the adhesive force promoting resin has a structure shown in a formula 1:

the UV color paste is a color paste for ultraviolet curing optical fiber coloring ink;

the preparation method of the self-initiated multifunctional epoxy acrylic resin comprises the following steps:

1) Adding a mol of AG-80 epoxy resin, b mol of 2-carboxyethyl acrylate and c mol of itaconic acid monoester into a reactor, uniformly stirring, adding a certain mass of N-vinyl monomer, adding a catalyst and a polymerization inhibitor, heating to 90-120 ℃, and reacting for 1-8 hours under the condition of heat preservation to obtain an epoxy acrylate intermediate; wherein, a (b + c) =1, 3.9-1, b: c = 1:1-3:1; the N-vinyl monomer accounts for 5-40% of the total mass of all the raw materials in the step, the dosage of the catalyst accounts for 0.1-0.5% of the total mass of all the raw materials in the step, and the dosage of the polymerization inhibitor accounts for 0.01-0.5% of the total mass of all the raw materials in the step;

2) Mixing a photoinitiator 2959 with the total mole number of c mol and a photoinitiator R-GEN 988 according to a certain proportion, adding diisocyanate with the mole number of c mol, uniformly stirring, adding dibutyltin dilaurate with the total mass of 0.01-0.2% of the total mass of the raw materials in the step, and reacting for 1 hour at the temperature of 60-80 ℃ to obtain a photosensitive intermediate;

3) Uniformly mixing the epoxy acrylate intermediate obtained in the step 1) with the photosensitive intermediate obtained in the step 2) according to the mass ratio of 2.5-2:1, and reacting for 1.5-2.5 hours at 60-80 ℃ to obtain the self-initiated multifunctional epoxy acrylic resin.

2. The specialty outer coating for a guide optical cable of claim 1 wherein said itaconic acid monoester includes but is not limited to one or more of monoalkyl itaconate and monocyclopolyalkyl itaconate in any proportion; the catalyst is 4-dimethylamino pyridine, and the polymerization inhibitor is p-hydroxyanisole; the diisocyanate includes but is not limited to 2,4 toluene diisocyanate and isophorone diisocyanate.

3. The special outer coating for a guidance and optical cable of claim 1, wherein said N-vinyl monomers include but are not limited to one or more of N-vinyl pyrrolidone, N-vinyl phthalimide, 3-acetyl-N-vinyl pyrrolidone, N-vinyl carbazole, N-vinyl caprolactam in any ratio; the molar ratio of the photoinitiator 2959 to the photoinitiator R-GEN 988 is 1:1-3:1.

4. The special outer coating layer for a guidance cable according to claim 1, wherein the adhesion promoting resin is prepared by a method comprising the steps of:

1) Adding d mol of norbornene-2-methylamine into a reactor filled with e mol of 2,4-toluene diisocyanate, stirring while adding, and reacting for 1-3 hours at the temperature of 20-30 ℃; wherein d is e =1:1;

2) F mol of N-hydroxyethyl acrylamide is continuously added into the reactor in the step 1), then catalyst dibutyltin dilaurate and polymerization inhibitor p-hydroxyanisole are added, the temperature is kept at 60-80 ℃ for reaction for 2-6 hours, and the adhesion promoting resin is obtained; wherein, e is f = 1:1-1.1, and the dosage of the catalyst and the polymerization inhibitor is 0.01-0.1 percent of the total mass of the norbornene-2-methylamine, the 2,4-toluene diisocyanate and the N-hydroxyethyl acrylamide.

5. The specialty outer coating for a guidance and optical cable of claim 1 wherein said acrylamide based monomer includes but is not limited to one or more of N-p-hydroxyphenyl acrylamide, N '-vinyl bisacrylamide, N-benzyl acrylamide, N-dimethylacrylamide, N-dimethylaminopropyl acrylamide, N-diethylacrylamide, N- [ tris (3-acrylamido propyl methyl ether) methyl ] acrylamide, N' - (butane-1,4-diyl) bisacrylamide, N-phenyl acrylamide, hexamethylene bisacrylamide in any proportion; the N-vinyl monomer is not limited to one or a mixture of more of N-vinyl pyrrolidone, N-vinyl o-phenyl imine, 3-acetyl-N-vinyl pyrrolidone, N-vinyl carbazole and N-vinyl caprolactam according to any proportion; the UV color paste is used for ultraviolet curing optical fiber coloring ink, is dispersed by using a UV monomer in advance, and is added with a proper amount of defoaming agent and dispersing agent.

6. A special outer coating layer for an optical guidance cable according to claim 5, characterized in that said UV monomers include but are not limited to one or a mixture of hexanediol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate in any proportion.

7. The preparation method of the special outer coating layer for the guidance optical cable, as recited in claim 1, is characterized in that the raw material components are weighed, stirred for 30-120 minutes at a rotation speed of 800-1500 rpm at about 60-80 ℃, mixed evenly, filtered by a 400-600 mesh filter, and placed in a 30-50 ℃ oven for deaeration for 8-15 hours to obtain the finished product of the special outer coating layer for the guidance optical cable.

8. A guidance cable using the special outer coating layer of claim 1.