CN107759926B - Flame-retardant smoke-suppression type PVC (polyvinyl chloride) with phosphomolybdate and preparation method thereof - Google Patents

Flame-retardant smoke-suppression type PVC (polyvinyl chloride) with phosphomolybdate and preparation method thereof Download PDF

Info

Publication number
CN107759926B
CN107759926B CN201711089431.XA CN201711089431A CN107759926B CN 107759926 B CN107759926 B CN 107759926B CN 201711089431 A CN201711089431 A CN 201711089431A CN 107759926 B CN107759926 B CN 107759926B
Authority
CN
China
Prior art keywords
phosphomolybdate
pvc
parts
flame
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201711089431.XA
Other languages
Chinese (zh)
Other versions
CN107759926A (en
Inventor
高明
李俊飞
岳丽娜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
North China Institute of Science and Technology
Original Assignee
North China Institute of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by North China Institute of Science and Technology filed Critical North China Institute of Science and Technology
Priority to CN201711089431.XA priority Critical patent/CN107759926B/en
Publication of CN107759926A publication Critical patent/CN107759926A/en
Application granted granted Critical
Publication of CN107759926B publication Critical patent/CN107759926B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/005—Methods for mixing in batches
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)

Abstract

The invention relates to the technical field of flame-retardant smoke-suppression PVC, in particular to flame-retardant smoke-suppression PVC with phosphomolybdate, which consists of 100 parts of PVC resin, 40 parts of plasticizer, 4 parts of stabilizer, 0.5 part of lubricant and 6 parts of flame-retardant smoke-suppression agent, wherein the flame-retardant smoke-suppression agent consists of 1.5 parts of phosphomolybdate and 4.5 parts of antimony trioxide, and the stabilizer consists of 2 parts of dibasic lead phosphite and 2 parts of tribasic lead sulfate, and the mass ratio is the proportion. The flame retardant, smoke suppression and thermal stability of the PVC prepared by mixing phosphomolybdate and antimony trioxide in a certain compounding ratio are improved.

Description

Flame-retardant smoke-suppression type PVC (polyvinyl chloride) with phosphomolybdate and preparation method thereof
Technical Field
The invention relates to the technical field of flame-retardant smoke-suppression PVC, in particular to flame-retardant smoke-suppression PVC with phosphomolybdate and a manufacturing method thereof.
Background
Polyvinyl Chloride (PVC) resin is a homopolymer of vinyl Chloride, and is a thermoplastic polymer material formed by polymerizing vinyl Chloride monomer. It is one of five general-purpose resins, and its yield is second only to polyethylene, and is the second place of plastic products. Polyvinyl chloride plastic is widely applied to various departments such as industry, agriculture, chemical industry, electronic and electric appliances, building industry and the like due to the advantages of excellent electrical property, chemical corrosion resistance, simple processing, low price, easy modification and the like. PVC can be divided into two main types of hard PVC and soft PVC, and hard PVC products are widely applied in the world, but soft PVC is widely applied in China. Most of the soft PVC products are applied to the production process of electronic and electric appliances, wires and cables and building materials, and because the materials have higher requirements on flame retardant property, the flame retardant treatment of the soft PVC is necessary. In addition, the smoke generation amount of PVC is large, and the PVC is famous in common plastic products, so that the PVC has a particularly important significance in smoke suppression treatment.
Antimony trioxide is one of the earliest inorganic flame retardants and is also the largest of the current antimony-based flame retardants. Antimony trioxide belongs to an auxiliary flame retardant, and when the antimony trioxide is singly used as a flame retardant to be added, an ideal flame retardant effect cannot be achieved, but when the antimony trioxide is compounded with a halogen compound to be used as the flame retardant, excellent flame retardant performance can be shown. The antimony trioxide may beMeanwhile, the flame retardant function is realized in gas phase and condensed phase relative materials. The flame resistance of the soft PVC can be improved only by adding antimony trioxide into the soft PVC, because the PVC can release HCl gas when being ignited, antimony-containing compounds can be combined with HCl to generate oxychloride, the oxychloride is heated to continue to decompose, and takes away a part of heat generated in the combustion process of a sample, and finally SbCl is generated3. Then SbCl3The Cl & lt + & gt is decomposed by heat to release Cl & lt + & gt free radicals, and the Cl & lt + & gt can be combined with H & lt + & gt and HO & lt + & gt free radicals in the flame to play a role in inhibiting the flame from spreading. Further SbCl3The steam density is high, and the steam covers the surface of the material in the combustion process of the sample, so that the combustible gas decomposed from the sample under heating can be inhibited from escaping from the material, and the material is effectively prevented from contacting with air, thereby playing a role in flame retardance on the sample.
Flame retardants commonly used in PVC contain the following elements: compounds containing antimony, tin, zinc, copper, iron, molybdenum, or the like. Antimony trioxide (Sb)2O3) The flame retardant effect on PVC materials is good, and the flame retardant effect is obvious because the flame retardant effect can be simultaneously realized on gas phase and condensed relative materials. However, antimony trioxide releases toxic gases when burned. It is therefore necessary to find flame retardants that can replace it.
Disclosure of Invention
The invention aims to solve the defect of poor flame-retardant smoke-suppression effect of PVC in the prior art, and provides flame-retardant smoke-suppression PVC with phosphomolybdate and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the flame-retardant smoke-suppression PVC with the phosphomolybdate is designed and comprises 100 parts of PVC resin, 40 parts of plasticizer, 4 parts of stabilizer, 0.5 part of lubricant and 6 parts of flame-retardant smoke suppressor, wherein the flame-retardant smoke suppressor comprises 1.5 parts of phosphomolybdate and 4.5 parts of antimony trioxide, and the stabilizer comprises 2 parts of dibasic lead phosphite and 2 parts of tribasic lead sulfate, and the proportion is mass ratio.
Preferably, the lubricant is zinc stearate.
Preferably, the plasticizer is dioctyl phthalate.
Preferably, the phosphomolybdate is one of zinc phosphomolybdate, calcium phosphomolybdate, iron phosphomolybdate, nickel phosphomolybdate and cobalt phosphomolybdate.
Preferably, the preparation method of the phosphomolybdate comprises the following steps: preparation method A, preparation method B, preparation method C, preparation method D or preparation method E;
the preparation method A comprises the following steps: respectively preparing saturated solutions of zinc sulfate and phosphomolybdic acid by using deionized water, pouring the two saturated solutions into a 100/ml beaker, stirring for 3 minutes by using a glass rod, filtering, and drying the obtained precipitate in an oven for 20 minutes to obtain zinc phosphomolybdate;
the preparation method B comprises the following steps: respectively preparing saturated solutions of calcium chloride and phosphomolybdic acid by using deionized water, pouring the two saturated solutions into a 100/ml beaker, stirring for 3 minutes by using a glass rod, filtering, and drying the obtained precipitate in an oven for 20 minutes to obtain calcium phosphomolybdate;
the preparation method C comprises the following steps: respectively preparing saturated solutions of ferric trichloride and phosphomolybdic acid by using deionized water, pouring the two solutions into a 100/ml beaker, stirring for 3 minutes by using a glass rod, filtering, and drying the obtained precipitate in an oven for 20 minutes to obtain iron phosphomolybdate;
the preparation method D comprises the following steps: respectively preparing saturated solutions of nickel sulfate and phosphomolybdic acid by using deionized water, pouring the two saturated solutions into a 100/ml beaker, stirring for 3 minutes by using a glass rod, filtering, and drying the obtained precipitate in an oven for 20 minutes to obtain nickel phosphomolybdate;
preparation method E: and (3) respectively preparing saturated solutions of cobalt chloride and phosphomolybdic acid by using deionized water, pouring the two saturated solutions into a 100/ml beaker, stirring for 3 minutes by using a glass rod, filtering, and drying the obtained precipitate in an oven for 20 minutes to obtain the cobalt phosphomolybdate.
The preparation method of the flame-retardant smoke-suppression PVC with phosphomolybdate comprises the following steps:
the method comprises the following steps: putting 100 parts of PVC resin into a container;
step two: 40 parts of plasticizer, 4 parts of stabilizer, 0.5 part of lubricant, 6 parts of flame retardant and smoke suppressant and 100 parts of PVC resin are mixed and stirred uniformly by a mixer;
step three: mixing the product obtained in the step two for 10min at the temperature of 155-160 ℃ by a mixer;
step four: transferring the product obtained in the third step into a flat vulcanizing machine, and carrying out hot pressing for 5-8 min at 160-170 ℃ and 10-12 MPa;
step five: and taking out the product obtained in the step four, and naturally cooling to obtain the flame-retardant smoke-suppression type PVC.
The invention provides flame-retardant smoke-suppression PVC with phosphomolybdate and a preparation method thereof, and the flame-retardant smoke-suppression PVC has the following beneficial effects:
1) the phosphomolybdate has a certain flame-retardant effect, and the phosphomolybdate reacts with Sb at a low addition amount2O3The flame retardant is compounded to be used as a flame retardant of PVC, so that a better flame retardant effect can be obtained than that of independently adding antimony trioxide;
2) phosphomolybdate is used as a smoke suppressant of PVC, and can play a good smoke suppression role when the PVC is added in an amount of 1.5 g;
3) phosphomolybdate and Sb2O3The compound is used as a flame retardant of PVC, so that the decomposition of PVC is delayed to a certain extent, and the thermal stability of a sample is improved.
Drawings
FIG. 1 is a schematic diagram of the synthetic route of the present invention;
FIG. 2 shows pure PVC, PVC/Sb2O3PVC/phosphomolybdic acid/Sb2O3Thermogravimetric analysis of (a);
FIG. 3 shows PVC, PVC/phosphomolybdic acid 1.5g/Sb2O3Thermogravimetric analysis of (a);
FIG. 4 shows PVC, PVC/Nickel phosphomolybdate/Sb2O3Thermogravimetric analysis of (a);
FIG. 5 shows PVC sample and PVC/Sb2O3PVC/Zinc phosphomolybdate/Sb2O3Thermogravimetric analysis of (a);
FIG. 6 shows PVC sample and PVC/Sb2O3PVC/cobalt phosphomolybdate/Sb2O3Thermogravimetric analysis of (a);
FIG. 7 shows PVC pure sample and PVC/Sb2O3PVC/iron phosphomolybdate/Sb2O3Thermogravimetric analysis of (a);
FIG. 8 shows PVC sample and PVC/Sb2O3PVC/calcium phosphomolybdate/Sb2O3Thermogravimetric analysis of (a).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Referring to fig. 1-8, a flame-retardant smoke-suppressing PVC with phosphomolybdate comprises 100 g of PVC resin, 40 g of plasticizer, 4g of stabilizer, 0.5g of lubricant, and 6 g of flame-retardant smoke-suppressing agent, wherein the flame-retardant smoke-suppressing agent comprises 1.5g of phosphomolybdate and 4.5 g of antimony trioxide, the stabilizer comprises 2 g of dibasic lead phosphite and 2 g of tribasic lead sulfate, the lubricant is zinc stearate, the plasticizer is dioctyl phthalate, and the phosphomolybdate is one of zinc phosphomolybdate, calcium phosphomolybdate, iron phosphomolybdate, nickel phosphomolybdate, and cobalt phosphomolybdate.
The preparation method of the phosphomolybdate comprises the following steps: preparation method A, preparation method B, preparation method C, preparation method D or preparation method E;
the preparation method A comprises the following steps: respectively preparing saturated solutions of zinc sulfate and phosphomolybdic acid by using deionized water, pouring the two saturated solutions into a 100/ml beaker, stirring for 3 minutes by using a glass rod, filtering, and drying the obtained precipitate in an oven for 20 minutes to obtain zinc phosphomolybdate;
the preparation method B comprises the following steps: respectively preparing saturated solutions of calcium chloride and phosphomolybdic acid by using deionized water, pouring the two saturated solutions into a 100/ml beaker, stirring for 3 minutes by using a glass rod, filtering, and drying the obtained precipitate in an oven for 20 minutes to obtain calcium phosphomolybdate;
the preparation method C comprises the following steps: respectively preparing saturated solutions of ferric trichloride and phosphomolybdic acid by using deionized water, pouring the two solutions into a 100/ml beaker, stirring for 3 minutes by using a glass rod, filtering, and drying the obtained precipitate in an oven for 20 minutes to obtain iron phosphomolybdate;
the preparation method D comprises the following steps: respectively preparing saturated solutions of nickel sulfate and phosphomolybdic acid by using deionized water, pouring the two saturated solutions into a 100/ml beaker, stirring for 3 minutes by using a glass rod, filtering, and drying the obtained precipitate in an oven for 20 minutes to obtain nickel phosphomolybdate;
preparation method E: and (3) respectively preparing saturated solutions of cobalt chloride and phosphomolybdic acid by using deionized water, pouring the two saturated solutions into a 100/ml beaker, stirring for 3 minutes by using a glass rod, filtering, and drying the obtained precipitate in an oven for 20 minutes to obtain the cobalt phosphomolybdate.
The preparation method of the flame-retardant smoke-suppression PVC with phosphomolybdate comprises the following steps:
the method comprises the following steps: putting 100 g of PVC resin into a container;
step two: 40 g of plasticizer, 4g of stabilizer, 0.5g of lubricant, 6 g of flame retardant and smoke suppressant and 100 g of PVC resin are mixed and stirred uniformly by a mixer;
step three: mixing the product obtained in the step two for 10min at the temperature of 155-160 ℃ by a mixer;
step four: transferring the product obtained in the third step into a flat vulcanizing machine, and carrying out hot pressing for 5-8 min at 160-170 ℃ and 10-12 MPa;
step five: and taking out the product obtained in the step four, and naturally cooling to obtain the flame-retardant smoke-suppression type PVC.
TABLE 1 Experimental apparatus
Figure BSA0000153421060000071
Experimental data:
TABLE 2 PVC/phosphomolybdate/Sb2O3Oxygen index of sample
Figure BSA0000153421060000072
As can be seen from Table 2, the oxygen index of pure PVC is 28.8, and Sb is added separately2O3Oxygen index at time 34.1; when the amount of the additive is 0.5g to 2.0g,the oxygen index change range of each group is as follows: phosphomolybdic acid/Sb in constant total amount2O3The oxygen index is 34.1-37.1, and when the addition amount of zinc phosphomolybdate, iron phosphomolybdate, nickel phosphomolybdate, cobalt phosphomolybdate and calcium phosphomolybdate is 1.5, the oxygen index of the sample is higher than that of Sb with the addition amount of 1.5g alone2O3The oxygen index of (c). But are each lower than the oxygen index of 1.5g of phosphomolybdic acid added. According to the analysis, the phosphomolybdate has a certain flame retardant effect, and the phosphomolybdate reacts with Sb at a low addition amount2O3The flame retardant is compounded to be used as a flame retardant for PVC, so that the flame retardant effect is better than that of singly adding antimony trioxide, but the flame retardant effect is not as good as that of adding phosphomolybdic acid.
TABLE 3 phosphomolybdate/Sb addition2O3Smoke density of PVC sample
Figure BSA0000153421060000081
As can be seen from the smoke density data in Table 3, the maximum smoke density and smoke density rating of the samples were lower than that of the PVC without smoke suppression and the PVC sample with antimony trioxide added alone when the amount of phosphomolybdate added was 1.5 g. When the addition amount of the phosphomolybdate is 1.5g, the maximum smoke density value is reduced to different degrees compared with the PVC sample which is not treated by the smoke-inhibiting phosphomolybdate; the smoke density grade is reduced to different degrees, and compared with PVC samples which are not subjected to smoke suppression treatment and are subjected to single antimony trioxide addition treatment, the smoke density grade of the PVC samples which are subjected to the smoke density grade treatment by adding 1.5g of zinc phosphomolybdate is reduced by 2.61 percent and 1.3 percent respectively; the smoke density rating is 9.42% and 8.20% lower for the sample treated with 1.5g of iron phosphomolybdate than for the PVC sample without smoke suppression and after antimony trioxide alone. The smoke density grades are respectively reduced by 9.42 percent and 8.20 percent when the samples are treated by cobalt phosphomolybdate with the addition of 1.5g and compared with PVC samples which are not subjected to smoke suppression treatment and samples which are treated by antimony trioxide; the smoke density grades are respectively reduced by 1.8 percent and 0.48 percent when the PVC sample is treated by calcium phosphomolybdate with the addition of 1.5g and compared with the PVC sample which is not subjected to smoke suppression treatment and the sample which is subjected to antimony trioxide treatment; the smoke density grade is respectively reduced by 1.8 percent and 1.12 percent when the PVC sample is treated by nickel phosphomolybdate with the addition of 1.5g and compared with the PVC sample which is not subjected to smoke suppression treatment and the sample which is subjected to antimony trioxide treatment; the phosphomolybdate is used as a smoke suppressant of PVC, and can play a good smoke suppression role when the PVC is added by 1.5 g.
FIG. 2 shows pure PVC, PVC/Sb under the above experimental conditions2O3Phosphomolybdic acid/Sb2O3Thermogravimetry (TG) versus temperature profile. As can be seen from the thermogravimetric curve of pure PVC in FIG. 2, the sample undergoes two weightlessness, the first sample begins to slowly weightlessness to 260 ℃ from about 220 ℃, then rapidly weightlessness to 340 ℃, and then the mass is maintained relatively constant, during the process, the degradation process of removing hydrogen chloride from PVC molecules should occur, and the hydrogen chloride is rapidly volatilized after being removed from PVC, so that the sample mass is rapidly reduced; and the second time, from about 440 ℃, the sample begins to slowly lose weight until 700 ℃, the weight loss is still continued, the process is to crack sample molecules to generate olefin small molecules to volatilize, and simultaneously the small molecules can be partially recombined to deposit and carbonize, so the mass change trend is relatively slow. Comparison of PVC/Sb in FIG. 3.4-12O3、PVC/Sb2O3The thermogravimetric curve shows that the PVC/Sb2O3Phosphomolybdic acid/Sb2O3The thermal degradation process is basically consistent with that of pure PVC, except that the weight loss speed and the residual mass percentage of the pure PVC are different, namely the residual carbon rate of the PVC subjected to flame retardant treatment and the PVC not subjected to flame retardant treatment after decomposition under the same test condition is different.
TABLE 4 pure PVC, PVC/Sb2O3PVC/phosphomolybdic acid/Sb2O3Thermogravimetric curve characteristic data comparison
Figure BSA0000153421060000101
As can be seen from the thermogravimetric curve characteristic data in Table 4, the PVC which had not been flame-retardant treated decomposed almost completely after burning (char yield 1.1%), and after flame-retardant treatment with Sb2O3The initial decomposition temperature of the PVC is increased by 7.05 ℃, and the carbon residue rate is increased to 5.51%; after addition of 1.4g and 1.5g of phosphomolybdic acid, the initial decomposition temperature is higher than Sb alone2O3The sample is increased and the carbon residue rate is higher than that of the sample with Sb added2O3The increase indicates that the flame retardant effect of the PVC is better due to the addition of the compound flame retardant of the phosphomolybdic acid and the antimony trioxide.
TABLE 5 PVC, PVC/phosphomolybdic acid 1.5g/Sb2O3Thermogravimetric curve characteristic data comparison
Figure BSA0000153421060000102
As can be seen from the thermogram in FIG. 3, PVC/phosphomolybdic acid 1.5g/Sb2O3The carbon rate of 5g decomposed under the experimental conditions is obviously higher than that of a pure PVC sample.
As can be seen from the thermogravimetric curve characteristic data in Table 5, PVC/phosphomolybdic acid 1.5g/Sb2O3The initial decomposition temperature of 5g is improved by 7.05 ℃ compared with that of a PVC pure sample, and the residual carbon rate is improved to 11.35 percent. It can be seen from this that phosphomolybdic acid reacts with Sb2O3The compound is used as a flame retardant of PVC, and the thermal stability of PVC samples is obviously improved.
TABLE 6 PVC, PVC/Nickel phosphomolybdate/Sb2O3、PVC/Sb2O3Thermogravimetric curve characteristic data comparison
Figure BSA0000153421060000111
From the thermogravimetric analysis curve in FIG. 4, PVC/Nickel phosphomolybdate/Sb2O3The sample curve is PVC/Sb after 300 DEG C2O3And the upper part of the PVC pure sample curve shows that the thermal stability is better than that of the PVC/nickel phosphomolybdate/Sb2O3The carbon residue rate is improved to 9.13 percent, and PVC pure samples and PVC/Sb are obtained according to the average ratio2O3The obtained effect is good. It can be seen that the addition of nickel phosphomolybdate significantly improved the thermal stability of the PVC samples.
As can be seen from the thermogram in figure 5,PVC/Zinc phosphomolybdate/Sb2O3The curve is always in PVC pure sample and PVC/Sb after 300 DEG C2O3The upper part of the curve shows that the thermal stability is higher than that of PVC pure sample and PVC/Sb2O3Good results are obtained.
TABLE 7 PVC pure samples, PVC/Sb2O3PVC/Zinc phosphomolybdate/Sb2O3Thermogravimetric curve characteristic data comparison
Figure BSA0000153421060000112
Table 7 shows the PVC samples, PVC/Sb2O3PVC/Zinc phosphomolybdate/Sb2O3The thermogravimetric data are compared to obtain that PVC/zinc phosphomolybdate/Sb can be seen from the characteristic data of the thermogravimetric curve in the table2O3The carbon residue rate is improved to 7.02 percent, which are respectively compared with PVC pure samples and PVC/Sb2O3A better effect is obtained. Therefore, the zinc phosphomolybdate can obviously improve the thermal stability of the PVC sample.
From the thermogram in FIG. 6, it can be seen that PVC/cobalt phosphomolybdate/Sb2O3The carbon remaining rate under the experimental conditions is higher than that of PVC pure samples and PVC/Sb2O3The thermal stability is shown to be lower than that of PVC pure sample or PVC/Sb2O3And (4) the process is good.
TABLE 8 PVC pure samples, PVC/Sb2O3Comparison of thermogravimetric Curve characteristics of PVC/cobalt phosphomolybdate/sb 2O3
Figure BSA0000153421060000121
Table 8 shows the results of the reaction of PVC/cobalt phosphomolybdate/Sb2O3Thermogravimetric curve characteristic data, PVC pure sample and PVC/Sb2O3And the thermogravimetric data are compared to obtain the PVC/cobalt molybdate/Sb which can be seen from the characteristic data of the thermogravimetric curve in the table2O3The carbon residue rate is improved to 9.13 percent, compared with PVC pure sample and PVC/Sb2O3A better effect is obtained. Therefore, the cobalt phosphomolybdate can obviously improve the thermal stability of the PVC sample.
Observe the thermogravimetric plot in FIG. 7Line-finding iron phosphomolybdate/Sb2O3The curve is always in pure PVC, PVC/Sb after 300 DEG C2O3The upper part of the curve shows that the thermal stability is higher than that of pure PVC and PVC/Sb2O3Good results are obtained.
TABLE 9 PVC pure samples, PVC/Sb2O3PVC/iron phosphomolybdate/Sb2O3Thermogravimetric curve characteristic data comparison
Figure BSA0000153421060000122
Table 9 shows the results for pure PVC, PVC/Sb2O3PVC/iron phosphomolybdate/Sb2O3The thermogravimetric data are compared to obtain that PVC/iron phosphomolybdate/Sb can be seen from the characteristic data of the thermogravimetric curve in the table2O3The carbon residue rate is improved to 18.40 percent, compared with pure PVC and PVC/Sb2O3The addition of (2) gives better results. Therefore, the iron phosphomolybdate can obviously improve the thermal stability of the PVC sample.
From the thermogram in FIG. 8, calcium phosphomolybdate/Sb was observed2O3The curve is always in pure PVC, PVC/Sb after 300 DEG C2O3The upper part of the curve shows that the thermal stability is higher than that of pure PVC and PVC/Sb2O3Good results are obtained.
TABLE 10 PVC samples, PVC/Sb2O3PVC/calcium phosphomolybdate/Sb2O3Thermogravimetric curve characteristic data comparison
Figure BSA0000153421060000131
Table 10 shows the results for pure PVC, PVC/Sb2O3PVC/calcium phosphomolybdate/Sb2O3The thermogravimetric data are compared to obtain that PVC/calcium phosphomolybdate/Sb can be seen from the characteristic data of the thermogravimetric curve in the table2O3The carbon residue rate is improved to 13.2 percent, compared with pure PVC and PVC/Sb2O3The addition of (2) gives better results. Therefore, the calcium phosphomolybdate can obviously improve the thermal stability of the PVC sample.
To summarize:
according to the analysis and comparison, the zinc phosphomolybdate, the nickel phosphomolybdate, the iron phosphomolybdate, the calcium phosphomolybdate and the cobalt phosphomolybdate which are obtained after modification treatment are added into the PVC in the addition amount of 1.5g, and the residual carbon rate is higher than that of pure PVC and Sb is added separately2O3The sample of (1). The carbon residue rate of pure PVC is 1.1 percent, and PVC/Sb2O35.51% calcium phosphomolybdate/Sb2O313.2% iron phosphomolybdate/Sb2O318.4O%, Nickel phosphomolybdate/Sb2O37.02% of zinc phosphomolybdate/Sb2O312.7% cobalt phosphomolybdate/Sb2O313.01%, indicating phosphomolybdate and Sb2O3The compound is used as a flame retardant of PVC, so that the decomposition of PVC is delayed to a certain extent, and the thermal stability of a sample is improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (6)

1. The flame-retardant smoke-suppression PVC with the phosphomolybdate is characterized by comprising 100 parts of PVC resin, 40 parts of plasticizer, 4 parts of stabilizer, 0.5 part of lubricant and 6 parts of flame-retardant smoke suppressor, wherein the flame-retardant smoke suppressor comprises 1.5 parts of phosphomolybdate and 4.5 parts of antimony trioxide, and the stabilizer comprises 2 parts of dibasic lead phosphite and 2 parts of tribasic lead sulfate, and the mass ratio of the stabilizer is.
2. The flame retardant, smoke suppressant PVC with phosphomolybdate according to claim 1 wherein said lubricant is zinc stearate.
3. The flame retardant, smoke suppressant PVC with phosphomolybdate according to claim 1 wherein said plasticizer is dioctyl phthalate.
4. The flame retardant, smoke suppressant PVC with phosphomolybdate according to claim 1 wherein said phosphomolybdate is one of zinc phosphomolybdate, calcium phosphomolybdate, iron phosphomolybdate, nickel phosphomolybdate, cobalt phosphomolybdate.
5. The flame retardant and smoke suppressant PVC with phosphomolybdate according to claim 1 or 4, wherein said phosphomolybdate is prepared by: preparation method A, preparation method B, preparation method C, preparation method D or preparation method E;
the preparation method A comprises the following steps: respectively preparing saturated solutions of zinc sulfate and phosphomolybdic acid by using deionized water, pouring the two saturated solutions into a 100/ml beaker, stirring for 3 minutes by using a glass rod, filtering, and drying the obtained precipitate in an oven for 20 minutes to obtain zinc phosphomolybdate;
the preparation method B comprises the following steps: respectively preparing saturated solutions of calcium chloride and phosphomolybdic acid by using deionized water, pouring the two saturated solutions into a 100/ml beaker, stirring for 3 minutes by using a glass rod, filtering, and drying the obtained precipitate in an oven for 20 minutes to obtain calcium phosphomolybdate;
the preparation method C comprises the following steps: respectively preparing saturated solutions of ferric trichloride and phosphomolybdic acid by using deionized water, pouring the two solutions into a 100/ml beaker, stirring for 3 minutes by using a glass rod, filtering, and drying the obtained precipitate in an oven for 20 minutes to obtain iron phosphomolybdate;
the preparation method D comprises the following steps: respectively preparing saturated solutions of nickel sulfate and phosphomolybdic acid by using deionized water, pouring the two saturated solutions into a 100/ml beaker, stirring for 3 minutes by using a glass rod, filtering, and drying the obtained precipitate in an oven for 20 minutes to obtain nickel phosphomolybdate;
preparation method E: and (3) respectively preparing saturated solutions of cobalt chloride and phosphomolybdic acid by using deionized water, pouring the two saturated solutions into a 100/ml beaker, stirring for 3 minutes by using a glass rod, filtering, and drying the obtained precipitate in an oven for 20 minutes to obtain the cobalt phosphomolybdate.
6. A method of making a flame retardant, smoke suppressant PVC with phosphomolybdate as claimed in claim 1 comprising the steps of:
the method comprises the following steps: putting 100 parts of PVC resin into a container;
step two: 40 parts of plasticizer, 4 parts of stabilizer, 0.5 part of lubricant, 1.5 parts of flame retardant and smoke suppressant and 100 parts of PVC resin are mixed and stirred uniformly by a mixer;
step three: mixing the product obtained in the step two for 10min at the temperature of 155-160 ℃ by a mixer;
step four: transferring the product obtained in the third step into a flat vulcanizing machine, and carrying out hot pressing for 5-8 min at 160-170 ℃ and 10-12 MPa;
step five: and taking out the product obtained in the step four, and naturally cooling to obtain the flame-retardant smoke-suppression type PVC.
CN201711089431.XA 2017-10-27 2017-10-27 Flame-retardant smoke-suppression type PVC (polyvinyl chloride) with phosphomolybdate and preparation method thereof Active CN107759926B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711089431.XA CN107759926B (en) 2017-10-27 2017-10-27 Flame-retardant smoke-suppression type PVC (polyvinyl chloride) with phosphomolybdate and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711089431.XA CN107759926B (en) 2017-10-27 2017-10-27 Flame-retardant smoke-suppression type PVC (polyvinyl chloride) with phosphomolybdate and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107759926A CN107759926A (en) 2018-03-06
CN107759926B true CN107759926B (en) 2020-10-02

Family

ID=61273262

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711089431.XA Active CN107759926B (en) 2017-10-27 2017-10-27 Flame-retardant smoke-suppression type PVC (polyvinyl chloride) with phosphomolybdate and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107759926B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109467845B (en) * 2018-10-23 2020-11-10 华北科技学院 Flame-retardant smoke-suppression PVC composite material and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101456999A (en) * 2008-12-30 2009-06-17 深圳市领亚电子有限公司 Low smoke high flame retardant polyvinyl chloride composition for wire cable and preparation method
CN101974187A (en) * 2010-11-15 2011-02-16 江苏宝源高新电工有限公司 90-DEG C insulation-grade low-smoke and low-halogen PVC retardant jacket material
CN107286494A (en) * 2016-03-31 2017-10-24 苏州奥凯高分子材料股份有限公司 Phosphomolybdic acid zinc fire-resistant smoke-inhibiting PVC sheet material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101456999A (en) * 2008-12-30 2009-06-17 深圳市领亚电子有限公司 Low smoke high flame retardant polyvinyl chloride composition for wire cable and preparation method
CN101974187A (en) * 2010-11-15 2011-02-16 江苏宝源高新电工有限公司 90-DEG C insulation-grade low-smoke and low-halogen PVC retardant jacket material
CN107286494A (en) * 2016-03-31 2017-10-24 苏州奥凯高分子材料股份有限公司 Phosphomolybdic acid zinc fire-resistant smoke-inhibiting PVC sheet material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"磷钼酸钙阻燃抑烟剂的制备和性能研究";魏昭荣等;《塑料工业》;20050131;第33卷(第1期);第52-54页 *

Also Published As

Publication number Publication date
CN107759926A (en) 2018-03-06

Similar Documents

Publication Publication Date Title
Cheng et al. Application of metallic phytates to poly (vinyl chloride) as efficient biobased phosphorous flame retardants
CN107286563A (en) A kind of expansion type flame retardant and its preparation and application for ABS electric switch outer covers
CN103923450A (en) Synergistic flame retardant metal ion treated montmorillonoid PC/ABS (polycarbonate/polyacrylonitrile) alloy material and preparation method of alloy material
Meng et al. Bio‐based Mg (OH) 2@ M‐Phyt: improving the flame‐retardant and mechanical properties of flexible poly (vinyl chloride)
CN109593266A (en) A kind of ultralow smoke density non-halogen flame-retardant cable and preparation method thereof
CN109824974A (en) A kind of halogen-free flame-retardant composite material and preparation method thereof of high flowing antibacterial
CN107759926B (en) Flame-retardant smoke-suppression type PVC (polyvinyl chloride) with phosphomolybdate and preparation method thereof
CN111019123B (en) Method for flame-retardant modification of polyamide 56 by biomimetic modification of Lehm stone/graphene oxide nano composite material
CN105778268A (en) Halogen-free flame-retardant nano-montmorillonite polypropylene composite material and preparation method therefor
Liu et al. Activated carbon spheres (ACS)@ SnO2@ NiO with a 3D nanospherical structure and its synergistic effect with AHP on improving the flame retardancy of epoxy resin
Shi et al. Fabrication of bismuth oxychloride nanosheets decorated with chitosan and phytic acid for improvement of flexible poly (vinyl chloride) flame retardancy
CN108623844A (en) DOPO-LDH composite fire retardants and preparation method thereof and halogen-free flame retardant ethylene propylene diene monomer (EPDM) material and its application
CN111849145B (en) Halogen-free flame-retardant thermoplastic polyurethane nano composite material and preparation method thereof
CN109467845B (en) Flame-retardant smoke-suppression PVC composite material and preparation method thereof
CN113429770A (en) Preparation method of efficient flame-retardant modified unsaturated polyester resin
CN109988411B (en) Flame-retardant smoke-suppression thermoplastic polyurethane antistatic composite material and preparation method thereof
CN117106255A (en) Resistance-stabilized PPTC (poly (phenylene terephthamide)) polymer composition and preparation method thereof
CN107163397A (en) Conductive polypropylene/nylon composite materials and preparation method thereof
CN104829943A (en) Fumed-silica-containing intumescent polypropylene flame retardant and preparation method of flame retardant
CN103709657A (en) Halogen-free flame retardant PC/PET alloy material and preparation method thereof
CN106674605B (en) A kind of PP environment-friendlyflame flame retardants and preparation method thereof
CN108976754A (en) A kind of anti-electrostatic fire retardant compound material and its preparation method and application
CN108276634A (en) A kind of soft type fire-resistant cable material and preparation method thereof
CN107987316A (en) A kind of anti-flaming smoke-inhibiting agent, its preparation method and PVC flame-retardant smoke inhibitions material prepared therefrom
CN103804819A (en) Antimony-free flame-retardant composite material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant