CN113403126A

CN113403126A - Environment-friendly flame-retardant water-blocking paste for communication optical cable and preparation method thereof

Info

Publication number: CN113403126A
Application number: CN202110635868.9A
Authority: CN
Inventors: 乔传威; 郑金周; 刘仲毅; 王静礼; 梁浩勇; 李卫东
Original assignee: Zhengzhou Oupushi Technology Co ltd
Current assignee: Zhengzhou Oupushi Technology Co ltd
Priority date: 2021-06-08
Filing date: 2021-06-08
Publication date: 2021-09-17
Anticipated expiration: 2041-06-08
Also published as: CN113403126B

Abstract

The application relates to the technical field of communication optical cables, in particular to an environment-friendly flame-retardant water-blocking paste for communication optical cables and a preparation method thereof. The preparation raw materials comprise the following components in parts by weight: 1-6 parts of inorganic thickening agent, 8-20 parts of gelling agent, 30-70 parts of base oil, 12-30 parts of flame retardant and 3-12 parts of other auxiliary agent; the inorganic thickening agent is modified sodium bentonite. In the environment-friendly flame-retardant water-blocking paste, a proper amount of quaternary ammonium salt modified sodium bentonite is adopted in raw materials, and the components and the proportion of the base oil are adjusted, so that the high-low temperature applicability of the environment-friendly flame-retardant water-blocking paste is obviously improved, the dropping point is higher, and the cone penetration is lower at normal temperature and at the temperature of minus 40 ℃. Meanwhile, the water resistance of the flame-retardant water-blocking paste is improved to a great extent by adopting the hydrogenated styrene-isoprene copolymer and a proper amount of modified silica gel as the gelling agent, and particularly, the water resistance of the flame-retardant water-blocking paste is further improved by compounding and using a proper amount of ethylene oxide/propylene oxide block copolyether, neutral barium dinonylnaphthalene sulfonate and other components.

Description

Environment-friendly flame-retardant water-blocking paste for communication optical cable and preparation method thereof

Technical Field

The application relates to the technical field of communication optical cables, in particular to an environment-friendly flame-retardant water-blocking paste for communication optical cables and a preparation method thereof.

Background

With the rapid development of the communication industry in China, the use amount of optical cables is increasing day by day. In the using process, the change of the surrounding environment of the optical cable can generate air pressure difference between the inside and the outside of the protective sleeve, so that moisture is diffused from the outside of the optical cable to the inside in a non-directional manner, and finally, the inside of the optical cable generates undesirable high humidity, so that the transmission performance of the optical cable is greatly damaged; meanwhile, water may enter the optical cable due to damage thereof, and flow to the hinge closure in a longitudinal direction, resulting in severe performance degradation. Therefore, it is required that the optical cable filling paste has excellent water blocking property.

The optical cable is subjected to hydrogen loss in a hydrogen evolution environment under the action of moisture and humidity, and the transmission performance of the optical cable information can be greatly reduced when the optical cable is further subjected to stress, corrosion and hydrogen loss. The most fatal phenomenon is that the spontaneous combustion phenomenon of the insulated wire core material caused by overlarge current between conductors of the optical cable due to instantaneous overload and overhigh voltage under the extremely severe high-temperature weather condition of the optical cable can completely lose the information transmission performance, and has very serious consequences on national construction and social life. Therefore, it is required that the optical cable filling paste has excellent flame retardant properties. Meanwhile, under the condition of spontaneous combustion, the optical cable filling paste is easy to run off at high temperature and drop to the field ground environment to cause land pollution, so that the invention focuses on environmental protection performance and has excellent biodegradability.

In the existing factice for filling the optical cable, common cable paste is mostly adopted to prevent the optical cable from water seepage and dampness, only the water blocking effect is achieved, related manufacturers or related products are not provided in the aspects of flame retardant performance and environmental protection performance, and the three performances are considered simultaneously.

Disclosure of Invention

In order to solve the technical problems, the invention provides an environment-friendly flame-retardant water-blocking paste which is prepared from the following raw materials in parts by weight:

1-6 inorganic thickening agents

8-20% of gelling agent

30-70 parts of base oil

12-30% of flame retardant

3-12 parts of other auxiliary agents;

the inorganic thickening agent is modified sodium bentonite.

As a preferable technical scheme, the modified sodium bentonite is quaternary ammonium salt modified sodium bentonite.

As a preferred embodiment of the present invention, the base oil includes trimellitate ester and pentaerythritol ester; preferably, the mass ratio of the trimellitate to the pentaerythritol ester is (25-35): (15-24).

As a preferable technical scheme, the kinematic viscosity of the pentaerythritol ester at 100 ℃ is 27-30 mm²/s。

As a preferred embodiment of the present invention, the gelling agent comprises a hydrogenated styrene-isoprene copolymer; preferably, the content of the hydrogenated styrene-isoprene copolymer accounts for 6-12 wt% of the total amount of the raw materials for preparing the environment-friendly flame-retardant water-blocking paste.

In a preferred embodiment of the present invention, the other auxiliary agent comprises ethylene oxide/propylene oxide block copolyether.

As a preferable technical scheme of the invention, the flame retardant is a mixture of an organic phosphate ester liquid flame retardant and a phosphorus-nitrogen flame retardant powder flame retardant.

As a preferred technical solution of the present invention, the other auxiliary agent comprises a smoke suppressor; the smoke suppressor consists of ferrocene, zinc molybdate, melamine hydroxystannate and zinc hydroxystannate; preferably, the weight ratio of the ferrocene, the zinc molybdate, the melamine hydroxystannate and the zinc hydroxystannate is 1:2:1: 1.

The second aspect of the present invention provides a method for preparing the environment-friendly flame retardant and water blocking paste, which comprises the following steps:

(1) according to the proportion, pumping the base oil into a grease making kettle, heating to 50-70 ℃, adding a gelling agent, continuously stirring, heating to 160-180 ℃, and transferring into a blending kettle;

(2) cooling the raw materials of the blending kettle to 130-140 ℃, adding an inorganic thickening agent, circulating the shearing machine for 2-4 hours, and adjusting the shearing pressure to 1.0-1.2 MPa;

(3) and then cooling to 70-80 ℃, adding other additives, continuously and circularly shearing for 0.5-2 hours, then reducing the shearing pressure to zero, adding the rest raw materials, continuously stirring, circulating for 1 hour, and performing aftertreatment to obtain the modified starch.

The third aspect of the invention provides the application of the environment-friendly flame-retardant water-blocking paste, which is applied to the technical field of communication optical cables.

Has the advantages that: in the environment-friendly flame-retardant water-blocking paste, a proper amount of quaternary ammonium salt modified sodium bentonite is adopted in raw materials, and the components and the proportion of the base oil are adjusted, so that the high-low temperature applicability of the environment-friendly flame-retardant water-blocking paste is obviously improved, the dropping point is higher, and the cone penetration is lower at normal temperature and at the temperature of minus 40 ℃. Meanwhile, the water resistance of the flame-retardant water-blocking paste is improved to a great extent by adopting the hydrogenated styrene-isoprene copolymer and a proper amount of modified silica gel as the gelling agent, and particularly, the water resistance of the flame-retardant water-blocking paste is further improved by compounding and using a proper amount of ethylene oxide/propylene oxide block copolyether, neutral barium dinonylnaphthalene sulfonate and other components. In addition, the mixture of the organic phosphate liquid flame retardant and the phosphorus-nitrogen flame retardant powder is adopted in the application, and the smoke suppressor consisting of ferrocene, zinc molybdate, melamine hydroxystannate and zinc hydroxystannate is compounded and used, so that the flame retardant property of the water-blocking paste is obviously improved by utilizing the mutual synergistic action of the two components, and the water-blocking paste has more excellent comprehensive performance.

Drawings

FIG. 1 is a diagram of a product of the environment-friendly flame-retardant water-blocking paste.

FIG. 2 is a diagram of a product of the environment-friendly flame-retardant water-blocking paste.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.

The kinematic viscosity is the ratio of the hydrodynamic viscosity to the fluid density rho at the same temperature, represents the physical quantity of component viscosity, and is obtained by testing according to the conventional mode in the field. The viscosity index is used herein to refer to the degree to which the viscosity of any fluid changes with temperature. The higher the viscosity index, the less temperature dependent the viscosity of the fluid and the less temperature sensitive the viscosity, as measured in a conventional manner.

The invention provides an environment-friendly flame-retardant water-blocking paste, which is prepared from the following raw materials in parts by weight:

1-6 inorganic thickening agents

8-20% of gelling agent

30-70 parts of base oil

12-30% of flame retardant

3-12 parts of other auxiliary agents;

the inorganic thickening agent is modified sodium bentonite.

In some embodiments, the modified sodium bentonite is a quaternary ammonium salt modified sodium bentonite. The new material of Zhejiang Hongyu, Inc. with code number HY738 can be selected.

In some embodiments, the base oil comprises trimellitate and pentaerythritol esters;

the pentaerythritol ester is POE (saturated polyol ester) formed by reacting pentaerythritol with high and low carbon fatty acids. In some embodiments, the pentaerythritol ester has a Viscosity Index (VI) of 120 to 125; further preferably, the kinematic viscosity of the pentaerythritol ester at 40 ℃ is 288-352 mm²S (preferably 320 mm)²S); more preferably, the kinematic viscosity of the rubber composition at 100 ℃ is 27-30 mm²S (preferably 29 mm)²S); preferably, the mass ratio of the trimellitate to the pentaerythritol ester is (25-35): (15-24). The code POE320 of Yingkou Star fire chemical Co., Ltd can be selected.

The trimellitate is saturated polyol ester formed by reacting trimellitic acid (namely 1,2, 4-benzene tricarboxylic acid) with high and low carbon fatty acid, and can be prepared by Yingkou Star flame chemical company Limited under the code number S150.

The applicant finds that when a proper amount of quaternary ammonium salt modified sodium bentonite is adopted in the raw materials of the environment-friendly flame-retardant water-blocking paste, and the components and the proportion of the base oil are adjusted, the high-temperature and low-temperature applicability of the environment-friendly flame-retardant water-blocking paste can be obviously improved, so that the environment-friendly flame-retardant water-blocking paste has a high dropping point and a low cone penetration at normal temperature and at-40 ℃. Particularly, when trimellitate and pentaerythritol ester are used as base oil, quaternary ammonium salt with the weight percent of 3-4 wt% is used for modifying the sodium bentonite, and the performance is particularly remarkably improved. The applicant speculates that the quaternary ammonium salt modified sodium bentonite has a low response speed to high-temperature stimulation due to the fact that the structure of the quaternary ammonium salt modified sodium bentonite contains a bentonite structure, and is relatively stable at high temperature. Meanwhile, the bentonite is uniformly dispersed in the system by the long-chain structure of the quaternary ammonium salt in the structure, the components in the system are entangled by the long polymer chain segment, and external stimulation is consumed by elastic deformation and other modes at low temperature, so that the stability of the flame-retardant water-blocking paste at low temperature is improved. Particularly, when the system contains trimellitate and pentaerythritol ester in a specific ratio as base oil, a branched chain structure in the base oil structure can be randomly inserted into the system, the branched chain structure and a quaternary ammonium salt structure in a modified sodium bentonite structure can firmly stabilize the rest components in the system in a formed space network, and external stimulation is consumed through the stable network, so that the high-temperature and low-temperature stability of the flame-retardant water-blocking paste is effectively improved. Moreover, the stable network structure also improves the microstructure density of the flame-retardant water-blocking paste to a great extent and obviously improves the water-blocking performance of the flame-retardant water-blocking paste.

In some embodiments, the gelling agent comprises a hydrogenated styrene-isoprene copolymer; preferably, the content of the hydrogenated styrene-isoprene copolymer accounts for 6-12 wt% of the total amount of the raw materials for preparing the environment-friendly flame-retardant water-blocking paste. The hydrogenated styrene-isoprene copolymer can form a gel state in a system, is beneficial to improving the dropping point of the hydrogenated styrene-isoprene copolymer and controlling oil separation, and can be selected from the products of China petrochemical ba Ling petrochemical company Limited under the code SEP YH-4010.

Further preferably, the gelling agent further comprises a modified silica gel; the addition of a proper amount of modified silica gel in the flame-retardant water-blocking paste is helpful for improving the insulating property and the damping property of the flame-retardant water-blocking paste, and the flame retardant property of the flame-retardant water-blocking paste can be improved to a great extent. The product JW-E600 code of Shenzhen Jinwang science and technology Limited can be selected.

In some embodiments, the other adjuvant comprises an ethylene oxide/propylene oxide block copolyether. Contain hydrophilic ether segment in the ethylene oxide/epoxypropane block copolyether structure in this application, still contain hydrophobic aliphatic alkyl chain simultaneously, have the surface tension who meets the end, help destroying the micelle that the emulsification formed in the system, avoid steam further toward the inside infiltration of cream, have superstrong hydrolytic resistance, can choose for use Qingdao furun chemical engineering ltd, code number DL-32 product.

The applicant finds that when the hydrogenated styrene-isoprene copolymer and a proper amount of modified silica gel are used as the gelling agent, the improvement of the water resistance of the flame-retardant water-resistant paste is greatly facilitated, and particularly when a proper amount of ethylene oxide/propylene oxide block copolyether is added into the system, the improvement of the water resistance is particularly remarkable. The hydrogenated styrene-isoprene copolymer structure contains a rigid benzene ring structure and a flexible aliphatic alkyl chain, and is easy to form a gel state when added into the system, which is beneficial to stabilizing other components in the system, so that the dropping point of the water-blocking paste is improved, and the phenomena of oil separation and the like in the high-temperature environment and the like are avoided. Meanwhile, as some components such as the micromolecule ester base oil, the modified sodium bentonite and the like in the system have certain hydrophilicity, water in the environment can permeate into the flame-retardant water-blocking paste and form a water-in-oil emulsifying structure, so that the water-blocking performance of the flame-retardant water-blocking paste is hindered, and the addition of the ethylene oxide/propylene oxide block copolyether is beneficial to destroying water-in-oil micelles formed in the system, preventing water molecules from further permeating, and even being beneficial to extruding the water molecules out of the system, so that the water-blocking performance of the flame-retardant water-blocking paste is improved. Further, the applicant found that when the system contains neutral barium dinonylnaphthalenesulfonate as an antirust agent, the water-blocking effect is more excellent.

In some embodiments, the flame retardant is a mixture of an organophosphate ester liquid flame retardant and a phosphorus-nitrogen based flame retardant powder flame retardant. The organic phosphate flame retardant is liquid, has high phosphorus content, and can be produced by Nanjing Spanish chemical industry with the code number of HR-105. The phosphorus-nitrogen flame retardant powder is powdery, has the same higher phosphorus content and good thermal stability, has high hydrophobicity, hydrolysis resistance, high temperature resistance, no migration and good carbon forming property, and can be produced by Nanjing Spire chemical industry with the code number of HR-202.

In some embodiments, the other adjunct comprises a smoke suppressant; the smoke suppressor consists of ferrocene, zinc molybdate, melamine hydroxystannate and zinc hydroxystannate; preferably, the weight ratio of the ferrocene, the zinc molybdate, the melamine hydroxystannate and the zinc hydroxystannate is 1:2:1: 1.

The flame retardant described in the application preferably adopts a mixture of an organic phosphate flame retardant and phosphorus-nitrogen flame retardant powder, and the flame retardant performance of the flame-retardant water-blocking paste is found to be remarkably improved. On one hand, the organic phosphate flame retardant has higher phosphorus content, and the heated degradation product of the organic phosphate flame retardant promotes the surface of the flame-retardant base material to be quickly dehydrated and carbonized, so that a carbonized layer is formed because the simple substance carbon does not generate the evaporative combustion and the decomposition combustion of flame. Meanwhile, due to the fact that the phosphine and nitrogen-containing components in the phosphorus-nitrogen flame retardant powder structure prevent further combustion in a condensed phase and a gas phase, synergy is achieved, and a better flame retardant effect is achieved. On the other hand, as the organic phosphate flame retardant is not a liquid flame retardant, and the phosphorus-nitrogen flame retardant powder is a powdery flame retardant, the components can be dispersed more uniformly when the raw materials of the flame-retardant water-blocking paste are prepared by blending, so that better uniformity and higher bulk density are realized, and the phosphorus-nitrogen flame retardant powder has better stability at high temperature and can not migrate due to factors such as high temperature, so that the flame-retardant effect is further improved in a synergistic manner. In addition, the smoke suppressor in the application consists of ferrocene, zinc molybdate, melamine hydroxystannate and zinc hydroxystannate, and the components can adsorb smoke particles generated by combustion when the combustion occurs, so that the smoke suppressor can be prevented from flying. Meanwhile, the adsorbed smoke dust particle components are beneficial to promoting the dehydration and carbonization speed of the surface of the water-blocking paste, and can be used for further thickening the thickness of a carbon layer formed by dehydration by virtue of the synergistic action of the smoke dust particle components, the organic phosphate flame retardant and the phosphorus-nitrogen flame retardant powder, so that the flame retardant performance of the water-blocking paste is further improved.

Other adjuvants in this application may be co-dispersants used to aid in the components of the homogeneous dispersion system such as gelling agents, base oils, flame retardants, smoke suppressants, and the like, including but not limited to propylene carbonate.

Other additives in the application can also be modified nano white carbon black, the modified nano white carbon black is preferably prepared by a meteorological method, the preferable particle size is 10-30 nm, the oil distribution of a system is favorably inhibited by utilizing a large number of microporous structures, and a WeifangHeng nano material product HS-9280 can be selected.

Other auxiliary agents in this application may also be antioxidants, including but not limited to 2, 6-di-tert-butyl-p-cresol (T501) and the like, which can absorb the radicals generated by decomposition in the system, thereby avoiding the destruction of the microstructure of the paste by these radicals.

Other adjuvants in this application may also be rust inhibitors, including but not limited to neutral barium dinonylnaphthalene sulfonate, with certain salt spray resistance, rust inhibition, and anti-emulsification properties.

The applicant finds that after a proper amount of modified nano white carbon black and propylene carbonate are added into the system, the flame retardant property and the water blocking property of the flame-retardant water blocking paste can be improved to a great extent. The propylene carbonate can improve the full dispersion among the raw materials in the system, so that the flame-retardant components and the components which are helpful for water resistance in the system can be distributed more uniformly and compactly. On one hand, the modified nano white carbon black avoids the entry and the migration of water vapor by utilizing a large number of gap structures on the structure, thereby being beneficial to improving the water resistance performance of the modified nano white carbon black. Certainly, the multi-gap structure is beneficial to adsorbing the small molecular ester base oil in the system, and unstable phenomena such as oil leakage and oil separation under the high-temperature environment and the like are avoided. On the other hand, a condensed phase is formed during combustion, so that heat is rapidly transferred, and the effects of heat conduction and temperature reduction are achieved, thereby further improving the flame-retardant smoke-eliminating effect.

Further, the preparation method of the environment-friendly flame-retardant water-blocking paste comprises the following steps:

(1) mixing trimellitate and pentaerythritol ester to obtain base oil, and feeding the base oil into a grease making kettle; heating to 60 deg.C, adding hydrogenated styrene-isoprene copolymer, stirring, heating to 170 deg.C, and transferring into blending kettle.

(2) Adding the modified silica gel into the blending kettle, and stirring for 30 minutes; opening water cooling, cooling to 130-140 ℃, closing the water cooling, adding the modified sodium bentonite and the propylene carbonate, opening the circulating shearing device after the modified sodium bentonite and the propylene carbonate are completely dispersed, adjusting the shearing pressure to 1.0-1.2 MPa, and shearing for 3 hours.

(3) Opening a water cooling device, cooling to 70-80 ℃, sequentially adding an antioxidant, an antirust agent and a demulsifier, continuously and circularly shearing for 1 hour, and then reducing the shearing pressure to zero.

(4) Sequentially adding the modified nano white carbon black, the organic phosphate flame retardant, the phosphorus-nitrogen flame retardant powder mixture and the smoke suppressor, and continuously circulating for 1 hour; homogenizing, degassing, and transferring into a finished product tank.

The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the following insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure include the demulsifier, i.e., the ethylene oxide/propylene oxide block copolyether; as the trimellitate esters described in the following examples and comparative examples, Kangkou starfire chemical Co., Ltd., code No. S150 was used.

Example 1

The embodiment provides an environment-friendly flame-retardant water-blocking paste, which comprises the following components in formula table 1:

TABLE 1

Composition (A)	Content (wt.)
		Modified sodium bentonite	3.5
Modified silica gel	4
		Trimellitic acid ester	33.2
Pentaerythritol ester	24
		Hydrogenated styrene-isoprene copolymer	9
Propylene carbonate	1.1
		Modified nano white carbon black	2
2, 6-di-tert-butyl-p-cresol	0.8
		Neutral barium dinonyl naphthalene sulfonate	0.7
Ethylene oxide/propylene oxide block copolyethers	0.2
		Organic phosphate flame retardant	16
Phosphorus-nitrogen flame-retardant powder mixture	3
		Smoke eliminating agent	2.5

Wherein, the modified sodium bentonite adopts Zhejiang Hongyu New Material Co., Ltd, code No. HY738 product; the modified silica gel is a product of Shenzhen Jinwang science and technology Limited, code JW-E600; the pentaerythritol ester adopts a POE320 product of Yingkou Star fire chemical industry Co., Ltd; the hydrogenated styrene-isoprene copolymer adopts a product of China petrochemical barrage petrochemical company Limited with the code SEP YH-4010; the modified nano white carbon black adopts the product of Weifang Hengxiao nano material Limited company with code HS-9280; the ethylene oxide/propylene oxide block copolyether is prepared by Qingdao Sofu Runzhi chemical technology, Inc., product number DL-32; the organic phosphate flame retardant is produced by Nanjing Sil chemical industry, and is a product with the code number of HR-105; the phosphorus-nitrogen flame-retardant powder mixture is produced by Nanjing Spanish chemical industry, and is a product with the code number of HR-202; the smoke suppressor is ferrocene: zinc molybdate: the mass ratio of the mixture of melamine hydroxystannate and zinc hydroxystannate is 1:2:1: 1.

The preparation method of the environment-friendly flame-retardant water-blocking paste comprises the following steps:

(2) Adding the modified silica gel into the blending kettle, and stirring for 30 minutes; opening water cooling, cooling to 135 ℃, closing the water cooling, adding the modified sodium bentonite and the propylene carbonate, opening the circulating shears after the modified sodium bentonite and the propylene carbonate are completely dispersed, adjusting the shearing pressure to 1.1MPa, and shearing for 3 hours.

(3) And opening a water cooling device, cooling to 75 ℃, sequentially adding an antioxidant, an antirust agent and a demulsifier, continuously and circularly shearing for 1 hour, and then reducing the shearing pressure to zero.

Example 2

The embodiment provides an environment-friendly flame-retardant water-blocking paste, which is prepared from the following components in formula table 2:

TABLE 2

Example 3

The embodiment provides an environment-friendly flame-retardant water-blocking paste, which comprises the following components in formula table 3:

TABLE 3

Composition (A)	Content (wt.)
		Modified sodium bentonite	3.6
Modified silica gel	4
		Trimellitic acid ester	32
Pentaerythritol ester	22.4
		Hydrogenated styrene-isoprene copolymer	10
Propylene carbonate	1.2
		Modified nano white carbon black	2.5
2, 6-di-tert-butyl-p-cresol	0.8
		Neutral barium dinonyl naphthalene sulfonate	0.7
Ethylene oxide/propylene oxide block copolyethers	0.3
		Organic phosphate flame retardant	17
Phosphorus-nitrogen flame-retardant powder mixture	3.5
		Smoke eliminating agent	2

Example 4

The embodiment provides an environment-friendly flame-retardant water-blocking paste, which comprises the following components in formula table 4:

TABLE 4

Composition (A)	Content (wt.)
		Modified sodium bentonite	3.7
Modified silica gel	3.5
		Trimellitic acid ester	31
Pentaerythritol ester	23.9
		Hydrogenated styrene-isoprene copolymer	9
Propylene carbonate	1
		Modified nano white carbon black	2.5
2, 6-di-tert-butyl-p-cresol	0.8
		Neutral barium dinonyl naphthalene sulfonate	0.8
Ethylene oxide/propylene oxide block copolyethers	0.3
		Organic phosphate flame retardant	17.5
Phosphorus-nitrogen flame-retardant powder mixture	3.5
		Smoke eliminating agent	2.5

Comparative example 1

The comparative example provides an environment-friendly flame-retardant water-blocking paste, and the preparation raw materials of the environment-friendly flame-retardant water-blocking paste comprise the following components in formula table 5:

TABLE 5

Wherein the modified silica gel is a product JW-E600 of Shenzhen Jinwang science and technology Limited company; the pentaerythritol ester adopts a POE320 product of Yingkou Star fire chemical industry Co., Ltd; the hydrogenated styrene-isoprene copolymer adopts a product of China petrochemical barrage petrochemical company Limited with the code SEP YH-4010; the modified nano white carbon black adopts the product of Weifang Hengxiao nano material Limited company with code HS-9280; the ethylene oxide/propylene oxide block copolyether is prepared by Qingdao Sofu Runzhi chemical technology, Inc., product number DL-32; the organic phosphate flame retardant is produced by Nanjing Sil chemical industry, and is a product with the code number of HR-105; the phosphorus-nitrogen flame-retardant powder mixture is produced by Nanjing Spanish chemical industry, and is a product with the code number of HR-202; the smoke suppressor is ferrocene: zinc molybdate: the mass ratio of the mixture of melamine hydroxystannate and zinc hydroxystannate is 1:2:1: 1.

(2) Adding the modified silica gel into the blending kettle, and stirring for 30 minutes; opening water cooling, cooling to 135 ℃, closing the water cooling, adding propylene carbonate, opening the circulating shearing device after complete dispersion, adjusting the shearing pressure to 1.1MPa, and shearing for 3 hours.

Comparative example 2

The comparative example provides an environment-friendly flame-retardant water-blocking paste, and the preparation raw materials of the environment-friendly flame-retardant water-blocking paste comprise the following components in formula table 6:

TABLE 6

Wherein, the modified sodium bentonite adopts Zhejiang Hongyu New Material Co., Ltd, code No. HY738 product; the modified silica gel is a product of Shenzhen Jinwang science and technology Limited, code JW-E600; the metallocene polydiene copolymer is a product of DaelimSynol 40, a code number of Shanghai Kunshen chemical industry Co., Ltd; the hydrogenated styrene-isoprene copolymer adopts a product of China petrochemical barrage petrochemical company Limited with the code SEP YH-4010; the modified nano white carbon black adopts the product of Weifang Hengxiao nano material Limited company with code HS-9280; the ethylene oxide/propylene oxide block copolyether is prepared by Qingdao Sofu Runzhi chemical technology, Inc., product number DL-32; the organic phosphate flame retardant is produced by Nanjing Sil chemical industry, and is a product with the code number of HR-105; the phosphorus-nitrogen flame-retardant powder mixture is produced by Nanjing Spanish chemical industry, and is a product with the code number of HR-202; the smoke suppressor is ferrocene: zinc molybdate: the mass ratio of the mixture of melamine hydroxystannate and zinc hydroxystannate is 1:2:1: 1.

(1) according to the proportion, the metallocene polydiene copolymer is injected into a grease making kettle; heating to 60 deg.C, adding hydrogenated styrene-isoprene copolymer, stirring, heating to 170 deg.C, and transferring into blending kettle.

(2) Adding the modified silica gel into the blending kettle, and stirring for 30 minutes; and opening water cooling, cooling to 1305 ℃, closing the water cooling, adding the modified sodium bentonite and the propylene carbonate, opening the circulating shears after the modified sodium bentonite and the propylene carbonate are completely dispersed, adjusting the shearing pressure to 1.1MPa, and shearing for 3 hours.

Comparative example 3

The comparative example provides an environment-friendly flame-retardant water-blocking paste, and the preparation raw materials of the environment-friendly flame-retardant water-blocking paste comprise the following components in formula Table 7:

TABLE 4

Composition (A)	Content (wt.)
		Modified sodium bentonite	3.7
Modified silica gel	3.5
		Trimellitic acid ester	31
Pentaerythritol ester	23.9
		Hydrogenated styrene-isoprene copolymer	9
Propylene carbonate	1
		Modified nano white carbon black	2.5
2, 6-di-tert-butyl-p-cresol	0.8
		Neutral barium dinonyl naphthalene sulfonate	0.8
Organic phosphate flame retardant	17.5
		Phosphorus-nitrogen flame-retardant powder mixture	3.5
Smoke eliminating agent	2.5

Wherein, the modified sodium bentonite adopts Zhejiang Hongyu New Material Co., Ltd, code No. HY738 product; the modified silica gel is a product of Shenzhen Jinwang science and technology Limited, code JW-E600; the pentaerythritol ester adopts a POE320 product of Yingkou Star fire chemical industry Co., Ltd; the hydrogenated styrene-isoprene copolymer adopts a product of China petrochemical barrage petrochemical company Limited with the code SEP YH-4010; the modified nano white carbon black adopts the product of Weifang Hengxiao nano material Limited company with code HS-9280; the organic phosphate flame retardant is produced by Nanjing Sil chemical industry, and is a product with the code number of HR-105; the phosphorus-nitrogen flame-retardant powder mixture is produced by Nanjing Spanish chemical industry, and is a product with the code number of HR-202; the smoke suppressor is ferrocene: zinc molybdate: the mass ratio of the mixture of melamine hydroxystannate and zinc hydroxystannate is 1:2:1: 1.

(3) And opening a water cooling device, cooling to 75 ℃, sequentially adding an antioxidant and an antirust agent, continuing to circularly shear for 1 hour, and then reducing the shear pressure to zero.

Comparative example 4

The comparative example provides an environment-friendly flame-retardant water-blocking paste, and the preparation raw materials of the environment-friendly flame-retardant water-blocking paste comprise the following components in formula table 8:

TABLE 8

Composition (A)	Content (wt.)
		Modified sodium bentonite	3.7
Modified silica gel	12.5
		Trimellitic acid ester	31
Pentaerythritol ester	23.9
		Propylene carbonate	1
Modified nano white carbon black	2.5
		2, 6-di-tert-butyl-p-cresol	0.8
Neutral barium dinonyl naphthalene sulfonate	0.8
		Ethylene oxide/propylene oxide block copolyethers	0.3
Organic phosphate flame retardant	17.5
		Phosphorus-nitrogen flame-retardant powder mixture	3.5
Smoke eliminating agent	2.5

Wherein, the modified sodium bentonite adopts Zhejiang Hongyu New Material Co., Ltd, code No. HY738 product; the modified silica gel is a product of Shenzhen Jinwang science and technology Limited, code JW-E600; the pentaerythritol ester adopts a POE320 product of Yingkou Star fire chemical industry Co., Ltd; the modified nano white carbon black adopts the product of Weifang Hengxiao nano material Limited company with code HS-9280; the ethylene oxide/propylene oxide block copolyether is prepared by Qingdao Sofu Runzhi chemical technology, Inc., product number DL-32; the organic phosphate flame retardant is produced by Nanjing Sil chemical industry, and is a product with the code number of HR-105; the phosphorus-nitrogen flame-retardant powder mixture is produced by Nanjing Spanish chemical industry, and is a product with the code number of HR-202; the smoke suppressor is ferrocene: zinc molybdate: the mass ratio of the mixture of melamine hydroxystannate and zinc hydroxystannate is 1:2:1: 1.

(1) mixing trimellitate and pentaerythritol ester to obtain base oil, and feeding the base oil into a grease making kettle; heating to 60 deg.C, stirring, heating to 170 deg.C, and transferring into blending kettle.

Comparative example 5

The comparative example provides an environment-friendly flame-retardant water-blocking paste, and the preparation raw materials of the environment-friendly flame-retardant water-blocking paste comprise the components in the following formula table 9:

TABLE 9

Composition (A)	Content (wt.)
		Modified sodium bentonite	3.7
Modified silica gel	3.5
		Trimellitic acid ester	31
Pentaerythritol ester	23.9
		Hydrogenated styrene-isoprene copolymer	9
Propylene carbonate	1
		Modified nano white carbon black	2.5
2, 6-di-tert-butyl-p-cresol	0.8
		Neutral barium dinonyl naphthalene sulfonate	0.8
Ethylene oxide/propylene oxide block copolyethers	0.3
		Organic phosphate flame retardant	17.5
Phosphorus-nitrogen flame-retardant powder mixture	3.5

Wherein, the modified sodium bentonite adopts Zhejiang Hongyu New Material Co., Ltd, code No. HY738 product; the modified silica gel is a product of Shenzhen Jinwang science and technology Limited, code JW-E600; the pentaerythritol ester adopts a POE320 product of Yingkou Star fire chemical industry Co., Ltd; the hydrogenated styrene-isoprene copolymer adopts a product of China petrochemical barrage petrochemical company Limited with the code SEP YH-4010; the modified nano white carbon black adopts the product of Weifang Hengxiao nano material Limited company with code HS-9280; the ethylene oxide/propylene oxide block copolyether is prepared by Qingdao Sofu Runzhi chemical technology, Inc., product number DL-32; the organic phosphate flame retardant is produced by Nanjing Sil chemical industry, and is a product with the code number of HR-105; the phosphorus-nitrogen flame-retardant powder mixture is produced by Nanjing Spanish chemical industry, and is a product with the code number of HR-202.

(4) Sequentially adding the modified nano white carbon black, the organic phosphate flame retardant and the phosphorus-nitrogen flame retardant powder mixture, and continuously circulating for 1 hour; homogenizing, degassing, and transferring into a finished product tank.

Comparative example 6

The comparative example provides an environment-friendly flame-retardant water-blocking paste, and the preparation raw materials of the environment-friendly flame-retardant water-blocking paste comprise the following components in formula table 10:

watch 10

Wherein, the modified sodium bentonite adopts Zhejiang Hongyu New Material Co., Ltd, code No. HY738 product; the modified silica gel is a product of Shenzhen Jinwang science and technology Limited, code JW-E600; the pentaerythritol ester adopts a POE320 product of Yingkou Star fire chemical industry Co., Ltd; the hydrogenated styrene-isoprene copolymer adopts a product of China petrochemical barrage petrochemical company Limited with the code SEP YH-4010; the ethylene oxide/propylene oxide block copolyether is prepared by Qingdao Sofu Runzhi chemical technology, Inc., product number DL-32; the organic phosphate flame retardant is produced by Nanjing Sil chemical industry, and is a product with the code number of HR-105; the phosphorus-nitrogen flame-retardant powder mixture is produced by Nanjing Spanish chemical industry, and is a product with the code number of HR-202; the smoke suppressor is ferrocene: zinc molybdate: the mass ratio of the mixture of melamine hydroxystannate and zinc hydroxystannate is 1:2:1: 1.

(4) Sequentially adding an organic phosphate flame retardant, a phosphorus-nitrogen flame retardant powder mixture and a smoke suppressor, and continuously circulating for 1 hour; homogenizing, degassing, and transferring into a finished product tank.

Performance testing

The applicant carried out the following performance tests on the anti-corrosive grease samples in the above examples and comparative examples, and the specific experimental items and test standards are shown in the following table 11:

TABLE 11 test items and test standards

Wherein:

a is attached: DC1000V with stylus contacts inserted into the sample, 10mm apart, 60s, 500M omega insulated.

Attached b: AC2500, stylus tip insertion sample, 10mm apart, 60s, leakage current 1 mA.

And (c) attached: putting 10g of the sample under flame for 10s, then removing the flame, extinguishing for 10s, putting the sample under the flame for 10s, removing the flame, and extinguishing for 10 s; while less smoke is visually observed.

Table 12 results of performance testing

Test items	Example 1	Example 2	Example 3	Example 4	Comparative example 1
						Cone penetration at rest (25 ℃,150g)1/10mm	323	328	331	319	329
Cone penetration of the working cone (-40 ℃,150g)1/10mm	128	132	135	130	143
						Dropping Point C	254	258	248	256	245
Flash point. C	292	294	292	296	292
						Steel mesh oil distribution (80 ℃,24 h)/wt%	0	0	0	0	0.4
The evaporation capacity (80 ℃,24 h)/wt%	0	0	0	0	0.1
						Water resistance (23 ℃,7 x 24h)	Can not be disintegrated	Can not be disintegrated	Can not be disintegrated	Can not be disintegrated	Can not be disintegrated
Insulation test (attached a)	By passing	By passing	By passing	By passing	By passing
						Pressure test (attached b)	By passing	By passing	By passing	By passing	By passing
Flame-retardant smoke-eliminating test (with c)	By passing	By passing	By passing	By passing	By passing
						Test items	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5	Comparative example 6
Cone penetration at rest (25 ℃,150g)1/10mm	320	319	341	320	338
						Penetration of non-working cone(-40℃,150g)1/10mm	148	138	147	130	146
Dropping Point C	254	251	242	257	246
						Flash point. C	296	291	290	295	290
Steel mesh oil distribution (80 ℃,24 h)/wt%	0	0.5	1.4	0	1.1
						The evaporation capacity (80 ℃,24 h)/wt%	0	0.3	0.8	0	0.6
Water resistance (23 ℃,7 x 24h)	Can not be disintegrated	Disintegration of the material	Disintegration of the material	Can not be disintegrated	Disintegration of the material
						Insulation test (attached a)	By passing	By passing	Do not pass through	By passing	Do not pass through
Pressure test (attached b)	By passing	By passing	Do not pass through	Do not pass through	Do not pass through
						Flame-retardant smoke-eliminating test (with c)	By passing	By passing	By passing	Do not pass through	By passing

From the experimental results, the environment-friendly flame-retardant water-blocking paste has excellent wide-temperature applicability; as shown by the water resistance test data in the table, the filling paste provided by the invention is not disintegrated after 7 days of tests, which shows that the filling paste provided by the invention has good water resistance. As can be seen from the insulation and voltage resistance test data in the table, the filling paste provided by the invention has good electrical property; as shown in the flame retardant test in the table, the filling paste has no excessive black smoke after being burned by flame, which shows that the filling paste provided by the invention has excellent flame-retardant smoke-eliminating property.

The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; as will be readily apparent to those skilled in the art from the disclosure herein, the present invention may be practiced without these specific details; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.

Claims

1. The environment-friendly flame-retardant water-blocking paste is characterized by comprising the following raw materials in parts by weight:

1-6 inorganic thickening agents

8-20% of gelling agent

30-70 parts of base oil

12-30% of flame retardant

3-12 parts of other auxiliary agents;

the inorganic thickening agent is modified sodium bentonite.

2. The environment-friendly flame-retardant water-blocking paste as claimed in claim 1, wherein the modified sodium bentonite is quaternary ammonium salt modified sodium bentonite.

3. The environmentally friendly flame retardant and water blocking paste of claim 1, wherein the base oil comprises trimellitate ester and pentaerythritol ester; preferably, the mass ratio of the trimellitate to the pentaerythritol ester is (25-35): (15-24).

4. The environment-friendly flame-retardant water-blocking paste as claimed in claim 3, wherein the kinematic viscosity of the pentaerythritol ester at 100 ℃ is 27-30 mm²/s。

5. The environmentally friendly, fire retardant and water blocking paste of claim 1 wherein the gelling agent comprises a hydrogenated styrene-isoprene copolymer; preferably, the content of the hydrogenated styrene-isoprene copolymer accounts for 6-12 wt% of the total amount of the raw materials for preparing the environment-friendly flame-retardant water-blocking paste.

6. The environmentally friendly flame retardant and water blocking paste of claim 1 wherein the other adjuvant comprises an ethylene oxide/propylene oxide block copolyether.

7. The environment-friendly flame-retardant water-blocking paste according to any one of claims 1 to 6, wherein the flame retardant is a mixture of an organic phosphate ester liquid flame retardant and a phosphorus-nitrogen flame-retardant powder flame retardant.

8. The environment-friendly flame-retardant water-blocking paste according to claim 7, wherein the other auxiliary agents comprise a smoke suppressor; the smoke suppressor consists of ferrocene, zinc molybdate, melamine hydroxystannate and zinc hydroxystannate; preferably, the weight ratio of the ferrocene, the zinc molybdate, the melamine hydroxystannate and the zinc hydroxystannate is 1:2:1: 1.

9. The preparation method of the environment-friendly flame-retardant water-blocking paste according to any one of claims 1 to 8, characterized by comprising the following steps:

10. The application of the environment-friendly flame-retardant water-blocking paste according to any one of claims 1 to 8 is characterized in that the paste is applied to the technical field of communication optical cables.