CN111320736B - Low-shrinkage cable material resin and preparation method thereof - Google Patents
Low-shrinkage cable material resin and preparation method thereof Download PDFInfo
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- CN111320736B CN111320736B CN202010206707.3A CN202010206707A CN111320736B CN 111320736 B CN111320736 B CN 111320736B CN 202010206707 A CN202010206707 A CN 202010206707A CN 111320736 B CN111320736 B CN 111320736B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3218—Polyhydroxy compounds containing cyclic groups having at least one oxygen atom in the ring
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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- C08L75/08—Polyurethanes from polyethers
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
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Abstract
The invention belongs to the field of new materials, and particularly relates to low-shrinkage cable material resin and a preparation method thereof. The method takes 1, 3-dioxane-5, 5-dimethyl- (9CI) derivative (A), 2-hydroxymethyl-1, 3-propylene glycol (B), epichlorohydrin (C) and diisocyanate (D) as raw materials, and prepares the novel low-shrinkage cable material resin containing the spiro orthoester structure through multi-step reactions such as ester exchange, ring opening, ring formation, polycondensation and the like, so that the method has the advantage of low volume shrinkage while effectively improving the insufficient wear resistance and oil resistance of the cable material, and can predict that the product has wide market space in the field of special cables, particularly 5G communication cables.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to low-shrinkage cable material resin and a preparation method thereof.
Background
As is well known, the formulation and products of low-smoke, low-halogen, low-acid and halogen-free flame-retardant cable materials have been developed at the end of 80 generations in China, some manufacturers have produced low-smoke halogen-free flame-retardant cable materials, but most of the low-smoke halogen-free flame-retardant cable materials have the problems of poor mechanical properties and processability and the like. The high-end cable materials used at present still rely on import to some extent.
However, the quality problem is more serious in the current situation of the cable industry in China, the wire and cable manufacturing industry is excessively developed in a rough manner, the total productivity of the wire and cable is seriously excessive, the utilization rate of common wire and cable production equipment is generally less than 40%, and the development speed of 5G cannot be matched possibly in the long run. At the same time, new generation cable providers should be more aggressive for the arrival of 5G networks. 4G large capacity expansion +5G starts to be used commercially in 2019, 5G starts to be used commercially in 2020 in large scale, and if an equipment provider can start to push out a new cable product in 2020 in large scale, not only is the breakthrough and growth of enterprise performance realized, but also the rapid landing of 5G application is accelerated. The arrival of 5G will stimulate the development of the global wire and cable industry. However, the first ten cable enterprises in China only occupy less than 10% of the market share in China, that is to say, the leadership enterprises have great development potential, and the market share in China can be improved first.
According to the national planning of the main application fields of the electric wire and the cable, such as electric power (new energy and smart power grids), rail transit, aerospace, ocean engineering and the like, the electric wire and cable industry in China has good prospect in the future, the upgrading trend of industrial products is obvious, and the required scale of the industry is expected to exceed 1.9 trillion yuan by 2024 years. The requirement of the high-end cable, especially the cable used for 5G communication, is more severe, and the variation of the shrinkage rate of the cable product will directly affect the accuracy of the product and the stability of the performance. Therefore, in order to match the development of 5G, the development of the low-shrinkage cable material is not slow and has great significance.
Disclosure of Invention
The invention aims to overcome the defects of poor wear resistance, poor oil resistance, large shrinkage rate and the like of the existing cable material, and provides a low-shrinkage cable material resin and a preparation method thereof, wherein 1, 3-dioxane-5, 5-dimethyl- (9CI) derivative (A), 2-hydroxymethyl-1, 3-propanediol (B), epichlorohydrin (C) and diisocyanate (D) are used as raw materials to prepare the novel low-shrinkage cable material resin containing a spiro orthoester structure, so that the novel low-shrinkage cable material resin has the advantage of low volume shrinkage rate while effectively improving the insufficient performances of the cable material such as wear resistance, oil resistance and the like, and can be expected to have wide market space in the field of special cables, particularly 5G communication cables.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the low-shrinkage cable material resin is characterized by having a structural formula as follows:
a preparation method of low-shrinkage cable material resin is characterized by comprising the following steps:
step (1): performing ester exchange reaction to obtain an intermediate product I;
step (2): performing ring opening reaction to obtain an intermediate product II;
and (3): performing cyclization reaction to obtain an intermediate product III;
and (4): performing ring opening reaction to obtain an intermediate product IV;
and (5): and performing polycondensation reaction to obtain the low-shrinkage cable material resin, namely the target product V.
Preferably, the step (1) is specifically:
1mol of 1, 3-dioxane-5, 5-dimethyl- (9CI) derivative (A), 0.5-1mol of 2-hydroxymethyl-1, 3-propanediol (B) and 1-3 wt% of potassium carbonate are mixed and dissolved in 20mol of organic solvent a, stirred for 3-5h at the temperature of 60-70 ℃, kept stand, filtered and distilled under reduced pressure at the temperature of 40 ℃ to obtain an intermediate product I;
the using amount of the potassium carbonate is 1-3 wt% of the mass of the A.
Preferably, the step (2) is specifically:
adding 1mol of I into a mixture containing 0.5 to 3 wt% of BF3Heating to 40-80 ℃ in 1-1.2mol of epichlorohydrin (C) of ether to react for 2-8 h; standing, and distilling at 40 ℃ under reduced pressure to obtain an intermediate product II;
the BF3The amount of the diethyl ether is 0.5-3 wt% of the mass of the compound I.
Preferably, the step (3) is specifically:
adding 1-1.2mol of sodium hydroxide into 1mol of II, stirring for 0.5-5h at 40-80 ℃, and washing for 3 times by deionized water to obtain an intermediate product III.
Preferably, the step (4) is specifically:
adding 1-5 parts by weight of 0.5-10% sodium hydroxide aqueous solution into 1 part by weight of III, and stirring at 30-90 deg.C for 0.5-10h to obtain intermediate product IV.
Preferably, the step (5) is specifically:
adding 1mol of IV, 0.5-0.8mol of diisocyanate and 0.1-5 wt% of catalyst into 30mol of organic solvent b, stirring for 2-8h at 30-70 ℃, filtering, carrying out reduced pressure evaporation, and carrying out vacuum drying to obtain low-shrinkage cable material resin, namely a target product V;
the amount of the catalyst is 0.1-5 wt% of the mass of the diisocyanate.
Preferably, the 1, 3-dioxane-5, 5-dimethyl- (9CI) derivative is 1, 3-dioxane-2, 2-diethoxy-5, 5-dimethyl- (9CI) or 1, 3-dioxane-2, 2-diphenoxy-5, 5-dimethyl- (9 CI).
Preferably, the organic solvent a is toluene or 1, 4-dioxane.
Preferably, the diisocyanate is a polyether diisocyanate or a polyester diisocyanate.
Preferably, the catalyst is dibutyltin dilaurate, stannous octoate, stannous chloride or triethylene diamine.
Preferably, the organic solvent b is chloroform, dichloromethane or butyl acetate.
A low shrink cable material sheath which characterized in that: the composite material comprises the following raw materials in parts by weight:
low-shrinkage cable material resin V40-60
LDPE resin 40
Flame retardant 3
Antioxidant 3
Filler 3
And a curing accelerator 3.
Preferably, the preparation method of the low-shrinkage cable material sheath comprises the following steps:
vacuum drying the raw materials for 24h, adding the raw materials into a high-speed mixer according to a formula, uniformly mixing, and then extruding and molding in a single-screw extruder;
the parameters of the single screw extruder are as follows: the length-diameter ratio is 20-30; a feed opening 130-140 ℃; the heating temperature of the machine body is 160-; the screw rotation speed is 40 r/min.
The low-shrinkage cable material resin provided by the invention has the following preparation process:
the invention has the beneficial effects that:
(1) the invention provides a preparation method of low-shrinkage cable material resin, which adopts 1, 3-dioxane-5, 5-dimethyl- (9CI) derivative (A), 2-hydroxymethyl-1, 3-propanediol (B), epichlorohydrin (C) and diisocyanate (D) as raw materials to prepare the novel low-shrinkage cable material resin containing a spiro orthoester structure, and gets rid of the complex synthesis of the traditional spiro orthoester and wide raw material sources.
(2) The invention provides a low-shrinkage cable material resin, wherein a target product contains a spiro orthoester structure which is positioned at a side chain position of a polyurethane chain structure, so that the reaction activity is higher, and the problem of volume shrinkage after the traditional cable material resin is processed and molded is favorably solved.
(3) The invention provides a low-shrinkage cable material resin, wherein a target product contains a polyurethane structure, and on one hand, the polyurethane prepolymer has strong selectivity and designability; on the other hand, the excellent physical properties of the polyurethane structure can endow the cable with better mechanical properties.
(4) The invention provides a low-shrinkage cable material resin, which is a polyurethane resin containing a spiro orthoester structure synthesized by adjusting a polymer structure through molecular design, integrates excellent performance of the polyurethane resin, and solves the problem of poor shrinkage resistance of the traditional cable material. The product is expected to have wide market space in the cable field.
The specific implementation mode is as follows:
the present invention will be described in detail with reference to examples. It is to be understood, however, that the following examples are illustrative of embodiments of the present invention and are not to be construed as limiting the scope of the invention.
Example 1
Step (1) 1mol of 1, 3-dioxane-2, 2-diethoxy-5, 5-dimethyl- (9CI) (A), 1mol of 2-hydroxymethyl-1, 3-propanediol (B) and 3 wt% of potassium carbonate are mixed and dissolved in 20mol of toluene, stirred for 3 hours at 70 ℃, kept stand, filtered and distilled under reduced pressure at 40 ℃ to obtain an intermediate product I (IR: 1204 cm)-1、1105cm-1: spiro-C-O-C-is present; 3315cm-1: -OH is present; 2963cm-1：-CH3Presence);
the using amount of the potassium carbonate is 3 wt% of the mass of 1, 3-dioxane-2, 2-diethoxy-5, 5-dimethyl- (9 CI).
Step (2) 1mol of I is added to a solution containing 3 wt.% of BF3Heating to 80 ℃ in 1.2mol of epichlorohydrin (C) of ether, and reacting for 2 h; standing, distilling at 40 deg.C under reduced pressure to obtain intermediate productII(IR：1204cm-1、1105cm-1: spiro-C-O-C-is present; 3393cm-1: -OH is present; 747cm-1: -C-Cl is present);
the BF3The amount of diethyl ether was 3 wt% based on the mass of I.
Step (3) adding 1.2mol of sodium hydroxide into 1mol of II, stirring for 0.5h at 80 ℃, washing for 3 times by deionized water to obtain an intermediate product III (IR: 1207 cm)-1、1106cm-1: spiro-C-O-C-is present; 3393cm-1: -OH disappearance; 747cm-1: -C-Cl disappearance; 913cm-1: epoxy generation).
Step (4) to 1 part by weight of III was added 1 part by weight of 10% aqueous sodium hydroxide solution, and the mixture was stirred at 90 ℃ for 0.5 hour to obtain intermediate IV (IR: 1207 cm)-1、1106cm-1: spiro-C-O-C-is present; 913cm-1: disappearance of epoxy groups; 3399cm-1: -OH formation).
Step (5) adding 1mol IV, 0.8mol polyether type diisocyanate and 5 wt% dibutyltin dilaurate into 30mol dichloromethane, stirring for 2h at 70 ℃, filtering, evaporating under reduced pressure, and drying in vacuum to obtain the low-shrinkage cable material resin, namely the target product V (IR: 1207 cm)-1、1106cm-1: spiro-C-O-C-is present; 1725cm-1: -C ═ O is present; 3399cm-1: -OH is reduced; 3273cm-1: -NH-generation);
the using amount of the dibutyltin dilaurate is 5 wt% of the mass of the polyether diisocyanate.
Examples 2-6, otherwise identical to example 1, differ as set forth in the following table:
the low-shrinkage cable material resin obtained in the specific example 1 is used as a base material of an application example, and is processed and molded to obtain a low-shrinkage cable sheath.
The flame retardant is magnesium hydroxide and aluminum hydroxide according to the mass ratio of 3: 1; the antioxidant is tetra [ beta- (3 ', 5 ' -di-tert-butyl-4 ' -hydroxyphenyl) propionic acid ] pentaerythritol ester; the filler is: nano titanium dioxide; the curing accelerator is N, N-dihydroxypropyl-p-toluidine.
Application example 1
A low-shrinkage cable material sheath is prepared by the following steps: the composite material comprises the following raw materials in parts by weight:
low-shrinkage cable material resin V60
LDPE resin 40
Flame retardant 3
Antioxidant 3
Filler 3
And a curing accelerator 3.
Vacuum drying the raw materials for 24h, adding the raw materials into a high-speed mixer according to a formula, uniformly mixing, and then extruding and molding in a single-screw extruder;
the parameters of the single screw extruder are as follows: an aspect ratio of 30; a feed opening is 130-DEG C; heating the machine body at 160 ℃ in a 1 region, 170 ℃ in a 2 region, 180 ℃ in a 3 region, 175 ℃ in a machine neck region and 165 ℃ in a machine head region; the screw rotation speed is 40 r/min.
Application examples 2 to 3 were the same as application example 1 except that the following table was used
Application examples comparative examples 1 to 2 were each compared with application example 1 except that:
practical example comparative example 1
A low-shrinkage cable material sheath comprises the following raw materials in parts by weight:
polyurethane cable material resin V60
LDPE resin 40
Flame retardant 3
Antioxidant 3
Filler 3
And a curing accelerator 3.
Vacuum drying the raw materials for 24h, adding the raw materials into a high-speed mixer according to a formula, uniformly mixing, and then extruding and molding in a single-screw extruder;
the parameters of the single screw extruder are as follows: an aspect ratio of 30; a feed opening is 130-DEG C; heating the machine body at 160 ℃ in a 1 region, 170 ℃ in a 2 region, 180 ℃ in a 3 region, 175 ℃ in a machine neck region and 165 ℃ in a machine head region; the screw rotation speed is 40 r/min.
Practical example comparative example 2
A cable material sheath comprises the following raw materials in parts by weight:
polyvinyl chloride/polyurethane (100/30) cable material resin V60
LDPE resin 40
Flame retardant 3
Antioxidant 3
Filler 3
And a curing accelerator 3.
Vacuum drying the raw materials for 24h, adding the raw materials into a high-speed mixer according to a formula, uniformly mixing, and then extruding and molding in a single-screw extruder;
the parameters of the single screw extruder are as follows: an aspect ratio of 30; a feed opening is 130-DEG C; heating the machine body at 160 ℃ in a 1 region, 170 ℃ in a 2 region, 180 ℃ in a 3 region, 175 ℃ in a machine neck region and 165 ℃ in a machine head region; the screw rotation speed is 40 r/min.
The performance tests of the low shrinkage cable materials prepared in the application examples 1 to 3 and the comparative examples 1 to 2 of the present invention were respectively determined, and the results are shown in table 1.
Table 1 physical test properties of the examples
Firstly, as can be seen from table 1, compared with the conventional cable material, the novel low-shrinkage cable material of the present invention has the advantages of expansibility and curing due to the spiro orthoester structure, and the overall volume shrinkage of the cured material is extremely low.
Secondly, compared with the existing common cable material, the low-shrinkage cable material of the invention inherits the advantages of the polyurethane cable material, increases the crosslinking density due to the ring-opening curing of the spiro orthoester, and has great advantages in wear resistance, oil resistance, thermal elongation, polyurethane cable material and polyvinyl chloride/polyurethane cable material.
In summary, compared with the existing common cable material, the novel low-shrinkage cable material provided by the invention has the advantages of mechanical properties of polyurethane materials, and also has extremely low curing shrinkage. In the field of novel cables, particularly 5G communication cables have wide market prospects.
The test method comprises the following steps:
(1) wear resistance: test method for abrasion resistance: pressing the material into a 3mm slice, weighing the weight to be accurate to 0.0001g, fixing the slice on a wear-resistant tester for 500 times of scraping, taking off the slice and weighing, wherein the difference of the mass of the slice before and after the scraping (namely the wear amount) can be used for evaluating the wear resistance of the material, and the smaller the wear amount is, the better the wear resistance of the material is.
(2) Oil resistance: the method is operated according to the steps of GB/T2951.21-2008. Oil resistance expression method: 5 is optimal and 1 is worst.
(3) Hot extensibility: the method is operated according to the steps of GB/T2951.21-2008. Method for expressing heat extensibility: 5 is optimal and 1 is worst.
(4) Volume curing shrinkage: placing the shrinkage tester and the test piece mold into a vacuum oven at 75 ℃ and 0.1MPa to degas for 20min to 30min, and removing air bubbles inside the high-performance insulating encapsulating material in the shrinkage tester and the test piece mold tester. And (3) placing the shrinkage tester and the test piece mold after vacuum defoaming into an oven, and curing for 4 hours at 115 ℃. The shrinkage was calculated from the dimensional change of the cured product in the shrinkage tester.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (3)
1. The low-shrinkage cable material resin is characterized by having a structural formula as follows:
the low-shrinkage cable material resin is prepared according to the following steps:
(1) 1mol of 1, 3-dioxane-5, 5-dimethyl- (9CI) derivative A, 0.5-1mol of 2-hydroxymethyl-1, 3-propanediol B and 1-3 wt% of potassium carbonate are mixed and dissolved in 20mol of organic solvent a, stirred for 3-5h at the temperature of 60-70 ℃, kept stand, filtered and distilled under reduced pressure at the temperature of 40 ℃ to obtain an intermediate product I;
the amount of the 1-3 wt% of potassium carbonate is based on the mass of A;
the 1, 3-dioxane-5, 5-dimethyl- (9Cl) derivative is 1, 3-dioxane-2, 2-diethoxy-5, 5-dimethyl- (9Cl) or 1, 3-dioxane-2, 2-diphenoxy-5, 5-dimethyl- (9 Cl);
the organic solvent a is toluene or 1, 4-dioxane;
(2) 1mol of intermediate I is added to a reaction mixture containing from 0.5 to 3% by weight of BF3Heating to 40-80 ℃ in 1-1.2mol of epichlorohydrin C of ether, and reacting for 2-8 h; standing, and distilling at 40 ℃ under reduced pressure to obtain an intermediate product II;
said 0.5-3 wt% BF3The amount of diethyl ether is based on the mass of the intermediate product I;
(3) adding 1-1.2mol of sodium hydroxide into 1mol of the intermediate product II, stirring for 0.5-5h at 40-80 ℃, and washing for 3 times by using deionized water to obtain an intermediate product III;
(4) adding 1-5 parts by weight of 0.5-10% sodium hydroxide aqueous solution into 1 part by weight of the intermediate product III, and stirring at 30-90 ℃ for 0.5-10h to obtain an intermediate product IV;
(5) adding 1mol of intermediate product IV, 0.5-0.8mol of diisocyanate and 0.1-5 wt% of catalyst into 30mol of organic solvent b, stirring for 2-8h at 30-70 ℃, filtering, evaporating under reduced pressure, and drying in vacuum to obtain a target product, namely the low-shrinkage cable material resin V;
the 0.1-5 wt% of the catalyst is based on the mass of diisocyanate;
the diisocyanate is polyether diisocyanate or polyester diisocyanate;
the catalyst is dibutyltin dilaurate, stannous octoate, stannous chloride or triethylene diamine;
the organic solvent b is chloroform, dichloromethane or butyl acetate.
2. The low-shrinkage cable material sheath prepared by using the low-shrinkage cable material resin as claimed in claim 1 as a raw material, wherein the low-shrinkage cable material sheath is characterized in that: the composite material comprises the following raw materials in parts by weight:
40-60 parts of low-shrinkage cable material resin V
40 parts of LDPE resin
3 portions of flame retardant
3 portions of antioxidant
3 portions of filler
3 parts of a curing accelerator.
3. The low-shrinkage cable material sheath according to claim 2, prepared by the following steps:
vacuum drying the raw materials for 24h, adding the raw materials into a high-speed mixer according to a formula, uniformly mixing, and then extruding and molding in a single-screw extruder; the parameters of the single screw extruder are as follows: the length-diameter ratio is 20-30; a feed opening 130-140 ℃; the heating temperature of the machine body is 160-; the screw rotation speed is 40 r/min.
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| US5494990A (en) * | 1994-04-04 | 1996-02-27 | Hodogaya Chemical Co., Ltd. | Thermoplastic polyurethane resin having broad rubbery-state region and process for producing the same |
| CN101654544A (en) * | 2009-09-21 | 2010-02-24 | 哈尔滨化工研究所 | Insulating encapsulating material |
| CN102181028A (en) * | 2011-03-10 | 2011-09-14 | 沈阳化工大学 | Preparation method for prepolymer of spiro-monomer with hydroxyl functional group and diisocyanate |
| CN105219339A (en) * | 2015-11-11 | 2016-01-06 | 华南农业大学 | A kind of UV solidifies liquid optical cement, its preparation method and application thereof |
| CN106795262A (en) * | 2014-08-11 | 2017-05-31 | 路博润先进材料公司 | Moisture infiltration thermoplastic polyurethane with high-fire resistance |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5494990A (en) * | 1994-04-04 | 1996-02-27 | Hodogaya Chemical Co., Ltd. | Thermoplastic polyurethane resin having broad rubbery-state region and process for producing the same |
| CN101654544A (en) * | 2009-09-21 | 2010-02-24 | 哈尔滨化工研究所 | Insulating encapsulating material |
| CN102181028A (en) * | 2011-03-10 | 2011-09-14 | 沈阳化工大学 | Preparation method for prepolymer of spiro-monomer with hydroxyl functional group and diisocyanate |
| CN106795262A (en) * | 2014-08-11 | 2017-05-31 | 路博润先进材料公司 | Moisture infiltration thermoplastic polyurethane with high-fire resistance |
| CN105219339A (en) * | 2015-11-11 | 2016-01-06 | 华南农业大学 | A kind of UV solidifies liquid optical cement, its preparation method and application thereof |
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